3,6-二叠氮基-1,2,4,5-四嗪的合成及理论研究

以3,6-双(3,5-二甲基吡唑基)-1,2,4,5-四嗪为原料, 经过肼解反应和重氮化反应, 制得了3,6-二叠氮基-1,2,4,5-四嗪(DAT). 在DFT-B3LYP/6-31G*水平下求得了DAT的分子几何、IR光谱和热力学性质. 计算模拟IR光谱和实测IR光谱的对比表明DAT在固态下不发生叠氮-四唑互变异构反应. 根据IR光谱计算了DAT的热容、焓、熵等热力学参数, 也给出了这些参数和温度T之间的函数关系. 在不破坏四嗪环和叠氮基的原则下通过构建等键反应求得了DAT的精确生成热为1088 kJ?mol^—1. 爆轰性能计算表明DAT爆速D＝8.45 km?s^－1, 爆压P＝31.3 GPa, 高于TNT和HMX.

Synthesis and Theoretical Studies of 3,6-Diazido-1,2,4,5-tetrazine

3,6-Diazido-1,2,4,5-tetrazine (DAT) has been synthesized from 3,6-bis(3,5-dimethylpyrazol-l- yl)-1,2,4,5-tetrazine by hydrazinolysis and diazotization. The molecular geometries, infrared vibrational spectra, and thermodynamic properties of DAT were calculated using the density functional theory (DFT) method at the B3LYP/6-31G* level. The investigation into simulation and experiment of IR spectra indicates that there exists no azido-tetrazole tautomerism in solid DAT. The thermodynamic parameters including heat capacities, entropies and enthalpies were calculated according to IR spectra, and also the polynomial functions between thermodynamic parameters and temperature were determined. The accurate heat of formation 1088 kJ?mol^－1 of DAT in gas phase was obtained via designed isodesmic reaction in which the tetrazine ring and the azide group have been kept. The data obtained from the present study show a satisfactory detonation performance, with detonation velocity D of 8.45 km?s^－1 and detonation pressure P of 31.3 GPa, both of which are higher than those of TNT and HMX counterparts.