An NMR study of the hydroxylamine‐induced denitration of nitrocellulose, nitroamylose and some model monosaccharide nitrate esters

The previously known method of partial denitration of trinitrocellulose by hydroxylamine in pyridine was further investigated by NMR and applied to trinitroamylose and several other monosaccharide nitrates to study its selectivity. The sites of denitration were determined in each case using 13C and 15N NMR and, in most cases, by 2D homo- and hetero-nuclear (15NOC1H and 13C1H) chemical shift correlations. The results indicate that denitration of the polysaccharide nitrates is a highly regiospecific reaction occurring at the 2-position only, whereas with the monosaccharide nitrates denitration takes place with less selectivity, at the 4-position predominantly, and to a lesser extent at the 3-position.