Liu Min-Hsien, Liu Chuan-Wen
Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Taoyuan, Taiwan, Republic of China.
J Mol Model. 2016 Jul;22(7):153. doi: 10.1007/s00894-016-3024-y. Epub 2016 Jun 10.
Two synthesis methods were investigated in this study in order to explore feasible reaction pathways to obtain the target DADNE product: (1) the nitration of tetrahalogen ethene and (2) the reaction of acetamidine hydrochloride with dicarbonyl dichloride. Through theoretical simulation, the findings revealed that synthesis was possible, starting from acetamidine hydrochloride in a hydrated environment, followed by subsequent reaction routes via cyclization of the methoxy-substituted acetamidine anion intermediate with oxalyl chloride to form 2-methoxy-2-methyl-imidazolan-4,5-dione, acid-catalyzed synthesis of 2-methylene-imidazolan-4,5-dione, nitration using nitric acid to obtain 2-dinitromethylene-imidazolan-4,5-dione, and hydrolysis to produce 1,1-diamino-2,2-dinitroethene. A total energy of 1048.4 kJ mol(-1) was needed to carry out the reaction according to calculation of the energy barriers at each stage, as shown by the reaction profiles.
本研究中研究了两种合成方法，以探索获得目标DADNE产物的可行反应途径：（1）四卤代乙烯的硝化反应和（2）盐酸乙脒与二羰基二氯的反应。通过理论模拟，研究结果表明，从盐酸乙脒在水合环境中开始合成是可能的，随后通过甲氧基取代的乙脒阴离子中间体与草酰氯环化形成2-甲氧基-2-甲基-咪唑烷-4,5-二酮，酸催化合成2-亚甲基-咪唑烷-4,5-二酮，用硝酸硝化得到2-二硝基亚甲基-咪唑烷-4,5-二酮，然后水解生成1,1-二氨基-2,2-二硝基乙烯。如反应剖面图所示，根据各阶段能垒的计算，进行该反应总共需要1048.4 kJ mol(-1)的能量。
