化学学报 ›› 2011, Vol. 69 ›› Issue (18): 2159-2165. 上一篇    下一篇

研究论文

新型多氮化合物1,1-偶氮-1,2,3-三唑的合成与性能研究

李玉川1,2,李生华1,祁才1,张慧娟2,朱梦宇*,2,庞思平*,1   

  1. (1北京理工大学材料学院 北京 100081)
    (2北京理工大学生命学院 北京 100081)
  • 收稿日期:2010-10-28 修回日期:2011-02-25 出版日期:2011-09-28 发布日期:2011-05-23
  • 通讯作者: 李玉川 E-mail:yuchuanyh@yahoo.com.cn
  • 基金资助:

    含四氮腙结构的高氮杂环化合物合成

Synthesis and Performance of A Novel Poly-nitrogen Compound 1,1-Azobis-1,2,3-triazole

Li Yuchuan1,2 Li Shenghua1 Qi Cai1 Zhang Huijuan2 Zhu Mengyu*,2 Pang Siping*,1   

  1. (1 School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081)
    (2 School of Life Science and Technology, Beijing Institute of Technology, Beijing 100081)
  • Received:2010-10-28 Revised:2011-02-25 Online:2011-09-28 Published:2011-05-23
  • Contact: LI Yu-Chuan E-mail:yuchuanyh@yahoo.com.cn

以1-氨基-1,2,3-三唑(1)为原料, 经二氯异氰尿酸钠(SDCI)氧化偶联合成了具有稳定N8结构(8个氮原子直接相连)和光致变色特性的新型多氮化合物1,1-偶氮-1,2,3-三唑(2), 通过IR, Raman, 1H NMR, 13C NMR, MS, 元素分析等手段对其进行了表征|分离出了偶合反应副产物1H-1,2,3-三唑(3)|推测了2的质谱裂解机理. 在DFT-B3LYP/6-31G*水平下对2的结构进行了计算, 理论计算结合实测数据比较表明: 单环中引入偶氮键能够有效增加多氮化合物的密度和生成热, 与3相比, 2密度增加37.6%, 生成热增加48.8%|在不同类型的偶氮三唑化合物中, 直接相连的氮原子数目越多含能性质越突出, 与3,3-偶氮-1,2,3-三唑(4)相比, 2 密度增加5.6%, 生成热增加51.0%.

关键词: 多氮化合物, 1,2,3-三唑, 氧化偶联, 合成, 性能, 机理, 理论计算

1,1-Azobis-1,2,3-triazole (2), a novel poly-nirogen compound with stable N8 structure (eight directly linked nitrogen atoms) and photochromism, has been synthesized from 1-amino-1,2,3-triazole (1) by the oxidative coupling reaction (sodium dichloroisocyanurate (SDCI) as the oxidant) and its structure were characterized by IR, Raman, 1H NMR, 13C NMR, MS and elementary analysis techniques. 1H-1,2,3-triazole (3) was separated as the by-product and the decomposed mechanism of 2 were presumed. The structure of 2 was also estimated by the density functional theory (DFT) method based on B3LYP/6-31G* basis set. By the theoretical results and experimental data, introduction of azo group into single-ring poly-nitrogen compounds can efficiently increase their density and heat of formation, by comparison with the performance of 3, the density and heat of formation of 2 increase 37.6% and 48.8% respectively|also the performance of different types of azobis-triazoles was compared, and the results indicated that the larger the number of directly linked nitrogen atoms, the more excellent its performance is, e.g. the density and the heat of formation of 2 increased by 5.6% and 51.0% respectively compared with 3,3-azobis-1,2,3-triazole (4).

Key words: poly-nitrogen compound, 1,2,3-triazole, oxidative coupling, synthesis, performance, mechanism, theoretical calculation