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有机化学 ›› 2008, Vol. 28 ›› Issue (03): 422-427. 上一篇    下一篇

研究论文

3,6-双(1H-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪的合成、表征及量子化学研究

王伯周*,a，来蔚鹏a，刘愆a，廉鹏a，薛永强b   

  1. (a西安近代化学研究所 西安 710065)
    (b太原理工大学化工学院 太原 030024)
  • 收稿日期:2007-07-06 修回日期:2007-08-20 发布日期:2008-03-18
  • 通讯作者: 王伯周

Synthesis, Characterization and Quantum Chemistry Study on 3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine

WANG Bo-Zhou*,a,LAI Wei-Penga,LIU Qiana,LIAN Penga,XUE Yong-Qiangb   

  1. (a Xi′an Modern Chemistry Research Institute, Xi′an 710065)
    (b College of Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024)
  • Received:2007-07-06 Revised:2007-08-20 Published:2008-03-18
  • Contact: WANG Bo-Zhou

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以三氨基胍硝酸盐、戊二酮为起始原料, 经缩合、氧化、取代等反应合成了3,6-双(1H-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz), 并通过元素分析、红外、核磁、差示扫描量热法(DSC)等分析手段对其进行了表征. 采用亚硝酸钠/乙酸代替了二氧化氮/N-甲基吡咯烷酮, 改进了氧化步骤, 降低了成本, 简化了合成工艺. 用B3LYP方法, 在6-31G(d,p)基组水平上对其性能进行了计算, 得到了其稳定的几何构型和键级; 在振动分析的基础上求得体系的振动频率、IR谱及不同温度下的热力学性质, 并得到了温度对热力学性能影响的关系式; 探讨了其热解机理, 推断出四唑环开环时的过渡态和活化能.

关键词: 热分解机理, 3,6-双(1H -1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪, 合成, 热力学性质, 几何构型, 量化计算

3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) was synthesized by triamino- guanidinium nitrate with 2,4-pentanedione of condensation, followed by oxidation and substitution reaction. The product was characterized by elemental analysis, IR, NMR and DSC. Instead of nitrogen dioxide/N-methylpyrrolidone, acetic acid/sodium nitrite was as oxidizer during the oxidation, thus the cost was reduced and the process was simplified. The theoretical properties of BTATz were estimated by a B3LYP method based on 6-31G(d,p) basis set. The stable geometric configuration and bond order were obtained. The vibrational frequencies, IR spectrum and thermodynamics properties under different temperatures were obtained from vibrational analysis, and the relationship between temperature and thermodynamics properties was deducted. Pyrolysis mechanism of BTATz was discussed, and the transition state and activation energy of ring opening reaction of the tetrazole were deducted.

Key words: 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine, synthesis, pyrolysis mechanism, theoretical calculation, thermodynamics property, geometric configuration