3,6-二氨基-1,2,4,5-四嗪的百克量合成、晶体结构和热行为  

Hectogram Quantity Synthesis,Crystal Structure and Thermal Behavior of 3,6-Diamino-1,2,4,5-tetrazine

作　　者：周诚[1] 王伯周[1] 王友兵[1] 潘清[1] 苏鹏飞[1] 康冰[1] 田宏远[1] 

机构地区：[1]西安近代化学研究所,陕西西安710065

出　　处：《火炸药学报》2014年第2期13-17,共5页Chinese Journal of Explosives & Propellants

基　　金：总装预研项目(51328050205);国防基础科研计划项目(B09201100051)

摘　　要：以3,6-双(3,5-二甲基吡唑)-1,2,4,5-四嗪为原料,合成了3,6-二氨基-1,2,4,5-四嗪(DATz),产率为98.7%,合成量为500g/批。采用核磁、红外光谱、质谱和元素分析等对产物的结构进行了表征。在N-甲基吡咯烷酮和水的混合溶剂中培养了DATz的单晶,用X-射线单晶衍射仪测定了晶体结构。采用DSC、TG-DTG和固体原位反应池/FT-IR联用等分析方法研究了DATz的热分解行为。结果表明,该晶体为正交晶系,属Cmcm空间群,晶体学参数为:a=0.9431(4)nm,b=0.7850(3)nm,c=0.6267(3)nm,V=0.464(3)nm3,Z=8,Dc=1.605g/cm3,μ=0.123mm-1,F(000)=232,R1=0.0407,wR2=0.1278。DATz的放热分解峰温度为342.17℃,热稳定性较好,可能的热分解机理为先发生四嗪环的开环反应,后进行取代基氨基的分解反应。3,6-Diamino-1,2,4,5-tetrazine （DATz） was synthesized using 3,6-bis（3,5-dimethylpyrazol-l-yl）-l, 2,4, 5-tetrazine as starting material, with yield of 98.7%. The synthesis quantity was 500g /batch. The structure of DATz was characterized by 1 H NMR, 13 C NMR, FT-IR, MS and elemental analysis. Its single crystal was cultured using the mixed solvent of N-methyl-2-pyrrolidone and water. The thermal decomposition behavior of DATz was studied by DSC, TG-DTG and the solid reaction cell in situ/RSFT-IR. The crystal structure was determined by a X- ray single crystal diffractometer. The results show that the crystal is orthorhombic system, space group Cmcm with crystal parameters ofa=0.9431（4）nm, b=0.7850（3）nm, c=0. 6267（3）nm,V=0.464（3）nm3, Z=8, Dc=1.605 g/cm3 ,μ =0. 123mm 1 , F（000）=232, R1 =0. 0407, wR2 =0. 1278. DATz has an exothermic decomposition peak with summit peak at 342.17 ℃ and better thermal stability. The thermal decomposition mechanism of DATz is first tetrazine ring breaking and then the decomoosition reactions of substituent amino.

关 键 词：物理化学 富氮化合物 3 6-二氨基-1 2 4 5-四嗪 合成 晶体结构 热行为 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]