Action of hydroxylamine hydrochloride in pyridine on mehtyl-B-D-glucoside tetranitrate.

by Clarence Egbert Stanley. Rooney

Institution: McGill University
Department: Department of Chemistry.
Degree: PhD
Year: 1952
Keywords: Chemistry.
Record ID: 1528396
Full text PDF: http://digitool.library.mcgill.ca/thesisfile123880.pdf


In a Ph.D. thesis submitted in 1946 G.H. Segall described a reaction between hydroxylamine hydrochloride in pyridine and cellulose trinitrate in which a stable cellulose “mono-oxime dinitrate” was formed. A gas, predominantly nitrous oxide but containing some nitrogen, was evolved. Segall also found that cellulose trinitrate reacted with free hydroxylamine in pyridine to yield one mole of nitrogen and a cellulose “dinitrate”. His attempts to discover whether the “labile” nitrate group occupied the second, third or sixth positions in the glucose units of the cellulose trinitrate led to indecisive results. In these circumstances Hayward reverted to a simpler, crystalline compound, methyl-ß-D-glucopyranoside tetranitrate, for his study of the denitrating action of the free base hydroxylamine in pyridine. Hayward in his Ph.D. thesis (1949) reported that 1.26 moles of nitrogen gas was evolved from each mole of the methyl-ß-D-glucoside tetranitrate and a syrupy mixture of methylglucoside di- and trinitrates was formed. The reaction seemed to follow the same mechanism as with cellulose trinitrate, but it was not specific for any one nitrate group. The present investigation was initiated to study the action of hydroxylrumine hydrochloride in pyridine on methyl-ß-D-glucoside tetranitrate, and parallels the work of Hayward on the system employing hydroxylamine as a free base.[...]