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

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P₂₍₁/c)的空间群结晶排列,晶体密度为1.787g/cm³。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。

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

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 P₂₍₁/c) with a crystal density of 1.787g/cm³.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.