有机化学 ›› 2008, Vol. 28 ›› Issue (04): 727-731. 上一篇    下一篇

研究简报

多叠氮基三唑类高氮化合物的合成与晶体结构

李生华a,庞思平*,b,李小童a,于永忠a,赵信歧a   

  1. (a北京理工大学材料科学与工程学院 北京 100081)
    (b北京理工大学生命科学与技术学院 北京 100081)
  • 收稿日期:2007-05-21 修回日期:2007-09-11 发布日期:2008-04-17
  • 通讯作者: 庞思平

Synthesis and Crystal Structure of Novel Highly Nitrogen-Containing Compound of Polyazidotriazole

LI Sheng-Huaa,PANG Si-Ping*,b,LI Xiao-Tonga,YU Yong-Zhonga,ZHAO Xin-Qia   

  • Received:2007-05-21 Revised:2007-09-11 Published:2008-04-17
  • Contact: PANG Si-Ping

2,5,2'-三氯-1,1'-偶氮-1,3,4-三唑(1)与叠氮化钠反应首次合成含有多叠氮和四氮烯(N—N=N—N)结构的高氮化合物2,5,2'-三叠氮-1,1'-偶氮-1,3,4-三唑(3). 在相同条件, 2,5,2',5'-四氯-1,1'-偶氮-1,3,4-三唑(2)与叠氮化钠反应没有得到2,5,2',5'-四叠氮-1,1'-偶氮-1,3,4-三唑(b), 而是得到其分解产物3,5-二叠氮基-1,2,4-三唑(4). 用X 射线单晶衍射测定了化合物34的晶体结构. 晶体2b通过分子间氢键的相互作用形成具有9元环的三聚体,并由于三唑环共轭体系使氮上的H原子具有酸性,从而导致互变现象发生.

关键词: 三唑, 高氮化合物, 晶体结构, 叠氮, 合成

2,5,2'-trichloro-1,1'-azo-1,3,4-triazole (1) was treated with sodium azide to afford a novel high nitrogen compound of polyazidotriazole involving a tetrazene (N—N=N—N) structure: 2,5,2'-triazido-1,1'- azo-1,3,4-triazole (3). Under the same condition, 2,5,2',5'-tetraazido-1,1′-azo-1,3,4-triazole (b) was not accomplished, whereas its decomposed product 3,5-diazido-1,2,4- triazole (4) has been obtained in an acceptable yield. The crystal structures of 3 and 4 have been determined by X-ray diffraction analysis. The crystal measurement of 4 showed that the annular tautomerism phenomenon was due to the NH acidity and the intermolecular hydrogen bonds leading to a trimer with a 9-membered cycle.

Key words: high nitrogen compound, triazole, azido, crystal structure, synthesis