Nitrolysis of CN Single Bonds and Chemistry of Nitro and Nitroso Groups

Abstract

Abstract : A general procedure for the preparation of nitramines from tertamines was developed. The best procedure calls for an initial transformation of the tertiary amine into a nitrosamine followed by oxidation to the nitramine. From tri-n-butyl amine and nitric and hydrochloric acids in acetic anhydride, di-n- butylnitrosamine was reproducibly obtained (60%). Other examples are discussed. Nitrosamines are routinely oxidized to nitramines in nearly quantitative yields. Conversion of a carboxyl into an amino group afforded l-nitro-2-aminopiperidine isolated as either its carbamate or urea derivative. This result has encouraged the exploration of alpha-aminonitramines (or selected derivatives) in synthesis of dense fused ring systems (cage compounds). Cyclic nitronic-carboxylic acid anhydrides is a thesis research area for a graduate student. A five membered and a six-membered (not confirmed) example have been prepared. An acyl derivative of the former readily polymerized, as expected, by spontaneous ring opening. The work is continuing. Sydnones are energetic compounds available from certain aryl isocyanides and nitroform.