880-09-1Relevant articles and documents
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Volkova et al.
, p. 577 (1978)
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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.
Syntheses and Structures of [CH2(NCnH2n)2]Mo(CO)4 (n = 4,5) Complexes with Bis(cycloamine) Ligands Easily Prepared from CH2Cl2
Kyran, Samuel J.,Sanchez, Sergio G.,Arp, Christopher J.,Darensbourg, Donald J.
, p. 3598 - 3602 (2015/08/06)
Dipyrrolidylmethane, CH2(pyr)2, and dipiperidylmethane, CH2(pip)2, are synthesized via the condensation of their respective secondary amine precursors and dichloromethane at room temperature in the absence of light. Their use as chelating ligands is shown by the isolation and complete characterization of [CH2(pyr)2]Mo(CO)4 and [CH2(pip)2]Mo(CO)4 complexes. X-ray analysis reveals the methylene bis(cycloamines) to possess a sharp bite angle between 61° and 63° and a strong steric impact on the surrounding carbonyl ligands as a result of their ring conformations. (Chemical Equation Presented).
