Gruhne Michael S, Lenz Tobias, Rösch Markus, Lommel Marcus, Wurzenberger Maximilian H H, Klapötke Thomas M, Stierstorfer Jörg
Department of Chemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5-13, D-81337 Munich, Germany.
Dalton Trans. 2021 Aug 21;50(31):10811-10825. doi: 10.1039/d1dt01898a. Epub 2021 Jul 22.
1- and 2-Nitratoethyl-5H-tetrazole (1-NET and 2-NET) were prepared through nitration of the respective alkyl alcohol using 100% nitric acid. A mixture of 1- and 2-hydroxyethyl-5H-tetrazole was obtained after alkylation of 1,5H-tetrazole. Also, a one-pot synthesis of 1-hydroxyethyl-5H-tetrazole was developed enabling the selective preparation of 1-NET. Both organic nitrates were characterized by H, C, and H-N HMBC NMR spectroscopy. In addition, calculations using the Hirshfeld method and the EXPLO5 code were performed. Principally, 20 energetic coordination compounds involving the d-metals Mn, Cu, Zn, and Ag, each structurally characterized by low temperature single crystal X-ray diffraction, were prepared based on 1-NET and 2-NET. Of these complexes, 18 were obtained as pure bulk materials, and therefore, characterized for impact, friction, and ball drop impact sensitivity, as well as electrostatic discharge and thermal stability using differential thermal analysis. Hot plate and hot needle tests were performed mostly showing strong deflagrations making the complexes candidates for green combustion catalysts. Furthermore, successful PETN initiation experiments were carried out for several complexes and all ECCs were investigated by laser ignition experiments.
1-和2-硝酸乙酯基-5H-四唑（1-NET和2-NET）通过使用100%硝酸对相应的烷基醇进行硝化制备。1,5H-四唑烷基化后得到1-和2-羟乙基-5H-四唑的混合物。此外，还开发了一锅法合成1-羟乙基-5H-四唑，能够选择性地制备1-NET。两种有机硝酸盐均通过H、C和H-N HMBC核磁共振光谱进行表征。此外，还使用Hirshfeld方法和EXPLO5代码进行了计算。原则上，基于1-NET和2-NET制备了20种涉及d-金属Mn、Cu、Zn和Ag的高能配位化合物，每种化合物均通过低温单晶X射线衍射进行结构表征。在这些配合物中，18种以纯块状材料形式获得，因此，使用差示热分析对其冲击、摩擦和落球冲击敏感性以及静电放电和热稳定性进行了表征。进行了热板和热针试验，结果大多显示出强烈的爆燃，这使得这些配合物成为绿色燃烧催化剂的候选物。此外，对几种配合物进行了成功的太安起爆实验，并通过激光点火实验对所有高能配位化合物进行了研究。
