基于C-Br键断裂还原反应合成含能化合物1,3,5-三硝基六氢嘧啶  

Synthesis of an Energetic Compound 1,3,5-Trinitrohexahydropyrimidine Based on Carbon-bromine Cleavage Reduction

作　　者：杨凯迪 毕福强[1,2] 翟连杰 张俊林[1] 霍欢[1] 薛琪[1] 王伯周[1,2] YANG Kai-di;BI Fu-qiang;ZHAI Lian-jie;ZHANG Jun-lin;HUO Huan;XUE Qi;WANG Bo-zhou(Xi′an Modern Chemistry Research Institute, Xi′an 710065, China;State Key Laboratory of Fluorine & Nitrogen Chemicals,Xi′an 710065, China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《火炸药学报》2021年第1期41-44,共4页Chinese Journal of Explosives & Propellants

基　　金：National Natural Science Foundation of China(No.21805224)。

摘　　要：以2-溴-2-硝基-1,3-丙二醇、叔丁胺及37%甲醛溶液为原料,通过缩合环化、硝化和NaBH4(或KI)作用下的C-Br选择性还原切断反应获得了含能化合物1,3,5-三硝基六氢嘧啶(TNHP),总收率33%(或21.11%)。通过红外、核磁、元素分析及质谱技术对TNHP及其合成中间体的结构进行了表征;通过X射线单晶衍射分析制备并测定了TNHP的单晶结构,同时以实验和理论方法进一步研究了其物理化学和爆轰性能。结果表明,TNHP在单斜晶系中以P_(2(1)/c)的空间群结晶排列,晶体密度为1.787g/cm^(3)。其热分解温度为150.6℃,计算生成焓、爆速和撞击感度分别为-50.49kJ/mol、8388m/s和22.5J,显示了其在炸药领域的潜在应用前景。Starting from 2-bromo-2-nitropropane-1,3-diol,tert-butylamine and 37%formaldehyde,an energetic compound of 1,3,5-trinitrohexahydropyrimidine(TNHP)was achieved with a total yield of 33%(or 21.11%)through a synthetic procedure including condensation-cyclization,nitration and NaBH4(or KI)carbon-bromine cleavage reduction.The structure of TNHP as well as its synthetic intermediates were characterized by IR,NMR,elemental analysis and MS techniques.The single crystal of TNHP was prepared and determined via X-ray single crystal diffraction analysis,its physicochemical and detonation properties were further studied by experimental and theoretical methods.The results show that TNHP crystallizes in monoclinic with the space group of P_(2(1)/c) with a crystal density of 1.787g/cm^(3).Its decomposition temperature is 150.6℃,and the calculated heat of formation,detonation velocity and impact activity are-50.49kJ/mol,8388m/s and 22.5J,respectively,indicating a potential application prospect in the field of explosives.

关 键 词：有机化学 1 3 5-三硝基六氢嘧啶 C-Br断裂还原 TNHP 能量特性 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]