3-氰基-5-氨基-1, 2, 4-1H-三唑的高效合成与热性能  

High efficient synthesis and thermal behavior of 3-cyano-4-amino-1,2,4-1H-triazole

作　　者：刘亚静[1,2] 汪营磊 赵宝东[1] 高福磊 陈斌 胡岚[3] LIU Ya-jing;WANG Ying-lei;ZHAO Bao-dong;GAO Fu-lei;CHEN Bin;HU Lan(Xi’an Modern Chemistry Research Institute,Xi'an 710065,China;State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi'an 710065,China;China Ordance Industrial Standardization Research Institute,Beijing 100089,China)

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065 [3]中国兵器工业标准化研究所,北京100089

出　　处：《高校化学工程学报》2021年第1期92-99,共8页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21875185,22005238)。

摘　　要：以3-甲酰胺基-5-氨基-1,2,4-1H-三唑为原料,经缩合、环化、酯化、氨化和氧化等反应获得目标化合物3-氰基-5-氨基-1,2,4-1H-三唑(ATCN),通过优化制约合成工艺的氧化反应体系、反应温度以及反应时间,将收率由文献值37.0%提高至81.6%。采用核磁共振(NMR)、红外吸收(IR)和元素分析等手段表征了结构,通过差示扫描量热法(DSC)和原位红外技术研究ATCN热分解和热裂解特性,并进行热分析动力学计算。结果表明,ATCN第1个热分解峰值温度为163.01℃,对应为氨基和氰基的断裂;第2个热分解峰值温度为244.29℃,对应为三唑环结构的裂解。此外,通过热力学参数计算获得ATCN第1个热分解过程的活化能、活化焓、活化吉布斯自由能和活化熵分别为156.21、153.26、109.80 kJ·mol^(-1)和103.40 J·K^(-1)·mol^(-1)。3-cyano-5-amino-1,2,4-1H-triazole(ATCN)was synthesized via condensation,cyclization,esterification,amination and oxidation with aminoguanidine bicarbonate as a raw material.The oxidation reaction system,temperature,and time was optimized as the key steps for ATCN synthesis,and the yield of ATCN was upgraded from 37.0%as reported to 81.6%.ATCN was characterized by nuclear magnetic resonance(NMR),infrared absorption spectrum(IR)and element analysis,and its thermal decomposition and pyrolytic properties were investigated by DSC and in-situ IR.The thermokinetic analysis results show that the first thermal decomposition peak temperature is 163.01℃,which is corresponding to the fracture of amino and cyano groups.The second thermal decomposition peak temperature is 244.29℃,which is related to the fracture of triazole ring.In addition,through thermodynamic calculation,the activation energy,activation enthalpy,activation Gibbs free energy and activation entropy of the first thermal decomposition process of ATCN are 156.21,153.26,109.80 kJ·mol^(-1) and 103.40 J·K^(-1)·mol^(-1),respectively.

关 键 词：3-氰基-5-氨基-1 2 4-1H-三唑 高效合成 热分解 原位热裂解 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术]