4164-31-2Relevant academic research and scientific papers
In situ generated amine as a Lewis base catalyst in the reaction of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study
Zhang, Yu,Chi, Guoli,He, Ying,Xu, Zishuai,Zhang, Luyao,Luo, Jun,Zhou, Baojing
supporting information, (2019/04/08)
The problem how ammonium nitrate affects the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) in nitric acid to prepare 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) has puzzled chemists for decades. In this paper, experimental work and theoretical calculation are described to investigate the long-standing challenge. The experiment results showed that ammonium nitrate or alkylammonium chlorides were in favor of the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX) but hindered the conversion of MNX to HMX. A plausible catalytic mechanism was proposed. In which ammonia or amines, in situ generated from the unfavorable balance with their salts, act as Lewis base catalysts. At the same time, the DFT computation results reveal that rigid bicyclic transition states established with 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane, ammonia (or amines) and three water molecules lead to very low activation energies. Then, a novel process for the preparation of MNX with excellent yield up to 78.5% was developed, which is free of the use of NaNO2 or N2O4 as nitroso resources.
Synthesis of N,N-dialkylnitramines from secondary ammonium nitrates in liquid or supercritical carbon dioxide
Kuchurov,Fomenkov,Zlotin
experimental part, p. 2058 - 2062 (2011/01/08)
An efficient explosion-proof method was developed for the preparation of N,N-dialkylnitramines by treatment of dialkylammonium nitrates with a mixture of nitric acid and acetic anhydride in the presence of ZnCl2 in liduid or supercritical carbon dioxide.
ELECTROCHEMICAL TRANSFORMATION OF N-NITROSODIALKYLAMINES INTO N-NITRAMINES AND β-KETONITROSAMINES
Masui, Masaichiro,Nose, Koichi,Tanaka, Aiko,Yamakawa, Eiko,Ohmori, Hidenobu
, p. 3758 - 3760 (2007/10/02)
Controlled potential electrolysis, based on the results of cyclic voltammetry, of simple dialkylnitrosamines such as N-nitrosodibutylamine and N-nitrosodicyclohexylamine in acetonitrile at a glassy carbon electrode resulted in the formation of the corresponding nitramines as the major products together with β-ketonitrosamines in which the carbonyl group is on the same side of the nitroso-oxigen atom.With N-nitrosopiperidine, one derived from a cyclic amine, N-nitropiperidine was formed similarly but the β-oxidized nitrosamine was not detected in the electrolysis solution.In deoxygenated acetonitrile, neither the nitramines nor the β-ketonitrosamines were obtained from the electrolysis. - Keywords: N-nitrosamines; N-nitramines; β-ketonitrosamines; anodic oxidation; cyclic voltammetry; controlled potential electrolysis
