74261-01-1Relevant academic research and scientific papers
Formation of a Bridged Peroxide from Thebaine and Tetranitromethane; X-Ray Crystal Structure of 8α,10α-Epidioxy-8,14-dihydro-14β-nitrothebaine
Allen, Robert M.,Gilmore, Christopher J.,Kirby, Gordon W.,McDougall, David J.
, p. 22 - 23 (1980)
Thebaine (1) rects with tetranitromethane in benzene in the presence of oxygen to give, as the major product, the bridged peroxide, 8α,10α-epidioxy-8,14-dihydro-14β-nitrothebaine (3), the structure of which has been determined by X-ray crystallography.
Synthesis from Thebaine of 10-Oxothebaine, Potentially a Precursor for κ-Selective Opiates
Henderson, Calum F.,Kirby, Gordon W.,Edmiston, John
, p. 295 - 298 (2007/10/02)
Thebaine 3 has been converted in an improved yield (72percent), with tetranitromethane, oxygen and ammonia, into the 14β-nitro 8α,10α-epidioxide 4, which reacted with base to give the known 14β-nitro-10-oxo compound 7.Reduction of this nitro compound with tributyltin hydride gave the 8β-hydroxy-10-oxodihydrothebaine 8, which was dehydrated with phosphorus oxychloride to give 10-oxothebaine 9.As expected, this conjugated diene reacted with but-3-en-2-one to form a Diels-Alder cycloadduct 10, the 10-oxo dirivative of thevinone 11, the precursor of a well known series of opiate analgesics.Unexpectedly, the epidioxide 4 was found to isomerise cleanly on activated alumina to give the 8α,10α-epoxy acetal 5, in which a peroxide oxygen has been inserted into the 7,8-bond of the bridged peroxide 4.
The Nitration of Thebaine with Tetranitromethane
Allen, Robert M.,Kirby, Gordon W.,McDougall, David J.
, p. 1143 - 1147 (2007/10/02)
Thebaine (1) reacts in methanol with tetranitromethane to give, as major product, 14β-nitrocodeinone dimethyl acetal (2a), which has been converted into, inter alia, 14β-nitrocodeinone (3a), 14β-aminocodeinone dimethyl acetal (2b), 14β-aminocodeinone (3b), and 14β-aminocodeine.The nitration of thebaine with tetranitromethane in benzene in the presence of oxygen takes a different course.The major product has been identified as the cyclic peroxide 8α,10α-epidioxy-8,14-dihydro-14β-nitrothebaine (5) by a series of degradations leading to new 10α-hydroxy- and 10-oxo-thebaine derivatives.
