Page 88 - 精细化工2020年第2期

第 37 卷第 2 期 精 细 化 工 Vol.37, No.2
202 0 年 2 月 FINE CHEMICALS Feb. 2020

功能材料
5-氰基-4-氨基咪唑的合成及其热性能

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赵宝东 ，闫峥峰 ，刘亚静 ，汪营磊 ，高福磊 ，肖 川
（1. 西安近代化学研究所，陕西 西安 710065；2. 中国兵器科学研究院，北京 100089）
摘要：咪唑基含能化合物是目前高能化合物的重要研究方向，而 5-氰基-4-氨基咪唑是设计、合成新型咪唑联四
唑类高能高氮化合物的关键中间体。以 5-甲酰胺基-4-氨基咪唑（AICON）为原料，经其与三氯氧磷（POCl 3 ）
的脱水反应获得了 5-氰基-4-氨基咪唑（AICN），通过优化反应体系、反应温度、反应时间以及物料物质的量比，
使得 AICN 的收率>65%，纯度（HPLC）>99.5%。此外，采用 NMR、IR 和元素分析对其进行了结构确证，利
用热重分析法研究其热性能。结果表明，AICN 的最佳反应条件为以 POCl 3 为脱水剂，n(AICON)∶n(POCl 3 )=1∶
10，反应升温模式为先快速升温至 80~85 ℃，维持反应 30 min，然后降温至 70~75 ℃，维持反应 1.0~1.5 h；AICN
在 40~1000 ℃温度区间存在两个失重过程，对应的热分解温度区间分别为 40~400 ℃和 400~1000 ℃、热失重分
别为 19.8%和 60.7%、热分解峰温分别为 256.5 和 698.4 ℃，表明其具有良好的热稳定性。
关键词：5-氰基-4-氨基咪唑；含能化合物；三氯氧磷；脱水反应；热稳定性；功能材料
中图分类号：O626 文献标识码：A 文章编号：1003-5214 (2020) 02-0290-05

Synthesis and thermal behavior of 5-cyano-4-aminoimidazole

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Zhao Baodong , Yan Zhengfeng , Liu Yajing , Wang Yinglei ,
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Gao Fulei , Xiao Chuan
（1. Xi'an Modern Chemistry Research Institute, Xi'an 710065, Shaanxi, China; 2. Academy of Ordnance Science,
Beijing 100089, China）
Abstract: Imidazole based energetic compounds are important research directions on high energy
compounds, and 5-cyano-4-aminoimidazole is the key intermediate for the design and synthesis of novel
tetrazoyl imidazole high energy and high nitrogen compounds. Target compound 5-cyano-4-aminoimidazole
(AICN) was obtained by dehydration reaction of 5-carboxamide-4-amino imidazole (AICON) with
phosphoryl trichloride (POCl 3). Through optimizing the reaction system, reaction temperature, reaction time
and molar ratio of reactants, the yield and HPLC purity of AICN achieved higher than 65% and 99.5%,
respectively. Besides, the target compound was characterized by NMR, IR and element analysis, and its
thermal properties were investigated by thermogravimetric analysis (TG). The results showed that the
optimum conditions for the synthesis of AICN were as follows: POCl 3 was used as dehydrant, molar ratio
of AICON to POCl 3 was 1∶10, and reaction heating mode was that the reaction was rapidly heated to
80~85 ℃, maintained for 30 min, and then cooled down to 70~75 ℃, maintained for 1.0~1.5 h. AICN had
two thermal weightlessness processes in the temperature range of 40~1000 ℃, the corresponding
decomposition temperature regions were 40~400 ℃ and 400~1000 ℃, the thermal weightlessness was
19.8% and 60.7%, and the peak values of thermal decomposition temperatures were 256.5 and 698.4 ℃,
respectively, which indicated that it had good thermal stability.
Key words: 5-cyano-4-aminoimidazole; energetic compounds; phosphoryl trichloride; dehydration reaction;
thermal stability; functional materials

收稿日期：2019-06-16; 定用日期：2019-08-27; DOI: 10.13550/j.jxhg.20190543
基金项目：国家自然科学基金（21875185，21173163）
作者简介： 赵宝东（1989—），男，博士，助理研究员。联系人：汪营磊（1983—），男，博士，副研究员，E-mail：wangyl204@163.com。