2134/34851
Peter Horsewood
Peter
Horsewood
The reactions of thebaine with C-nitroso-compounds
Loughborough University
2018
untagged
Chemical Sciences not elsewhere classified
2018-09-13 07:52:17
Thesis
https://repository.lboro.ac.uk/articles/thesis/The_reactions_of_thebaine_with_C-nitroso-compounds/9396476
The reactions of thebaine with nitrosoarenes to form Diels–Alder adducts
have been investigated. Reversibility of the addition of a series of parasubstituted
nitrosoarenes to thebaine has been qualitatively studied by NMR spectrometry. The direction of the addition was found to be highly
stereospecific giving adducts that were readily hydrolysed to previously
inaccessible 14-aminocodeinone derivatives. No adducts of nitrosoalkanes
with thebaine could be prepared but the parent codeinone corresponding to
a formal addition of monomeric hyponitrous acid to thebaine was readily
formed by reaction of the latter with 1-chloro-1-nitrosocyclohexane in
acid solution.
Nitrosyl cyanide, formed from reaction of nitrosyl chloride with silver cyanide, was found to react with thebaine to give a normal adduct. With
the dienophile in excess an N-cyanomethylnorthebaine-nitrosyl cyanide
adduct was obtained. Evidence for the existence and structure of nitrosyl
cyanide was investigated further by undertaking a study of its reactions
with other conjugated dienes to give N-cyano-1,2-oxazines. The visible
spectrum of the green gaseous products from reaction of nitrosyl chloride with silver cyanide showed an n → π* transition with a maximum
absorption at 738 nm. This is a typical absorption maximum for a blue
monomeric nitrosoalkane.