TDNAZ·HNO3和DNAZ·HCl的结构及性能

钝感高能炸药1,3,3-三硝基氮杂环丁烷(TNAZ)可由3,3-二硝基氮杂环丁烷(DNAZ)进行合成. 在合成DNAZ的过程中, 得到了中间产物N-叔丁基-3,3-二硝基氮杂环丁烷硝酸盐(TDNAZ·HNO3)和3,3-二硝基氮杂环丁烷盐酸盐(DNAZ·HCl). 培养了二者的单晶, 并通过X射线单晶结构分析法测定了它们的晶体结构. TDNAZ·HNO3属于正交晶系, Pnma空间群, 晶胞参数a=1.2697(3) nm, b=0.8179(2) nm, c=1.1621(3) nm, V=1.2067 nm3, Z=4. DNAZ·HCl属于正交晶系, Cmc21空间群, 晶胞参数a=0.6681(2) nm, b=1.0441(2) nm, c=0.9971(2) nm, V=0.6955 nm3, Z=4. 用密度泛函理论方法对该二种化合物进行了几何优化和频率计算, 获得分子结构、原子上Hirshfeld电荷、原子间Mayer键级和前沿轨道能量及组成. 基于分子和电子结构信息从理论上解释了相关反应机理, 并对两种化合物的热稳定性进行了比较.

Structure-Property Investigation on TDNAZ·HNO3 and DNAZ·HCl

1,3,3-Trinitroazetidine(TNAZ) is one of famous insensitive and high energetic materials, which can be synthesized by 3,3-dinitroazetidine(DNAZ). N-Tertiarybutyl-3,3-dinitroazetidine nitrate(TDNAZ·HNO3) and 3,3-dinitroazetidine hydrochloride(DNAZ·HCl) were synthesized during the process of synthesizing DNAZ. Single crystals suitable for X-ray measurement were obtained. TDNAZ·HNO3 crystallizes in the orthorhombic system, space group Pnma with unit cell parameters a=1.2697(3) nm, b=0.8179(2) nm, c=1.1621(3) nm, V=1.2067 nm3 , Z=4. DNAZ·HCl crystallizes in the orthorhombic system, space group Cmc21 with unit cell parameters a=0.6681(2) nm, b=1.0441(2) nm, c=0.9971(2) nm, V=0.6955 nm3, Z=4. The Density-Functional Theory(DFT) method was used to calculate the geometry and frequencies of the two intermediates. The geometry, Hishfeld charges of atoms, Mayer bond orders, frontier orbital energy and the main atomic orbital percentage were calculated. The corresponding reaction mechanism was explained based on the molecular and electronic structural information. The thermal stability was also compared by their thermal behavior.