多取代芳基重氮盐环合芳基五唑的过程研究  

Study on process for cycloaddition synthesis of aryl pentazole from multi substituted aryl diazonium salt

作　　者：刘力乐 秦丰 王钲鑫 王鹏飞 胡炳成[1] 孙呈郭[1] LIU Li-le;QIN Feng;WANG Zheng-xin;WANG Peng-fei;HU Bing-cheng;SUN Cheng-guo(School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]南京理工大学化学与化工学院,江苏南京210094

出　　处：《现代化工》2024年第S02期140-145,共6页Modern Chemical Industry

基　　金：国家自然科学基金(11972178,22205109)。

摘　　要：重氮盐与叠氮化合物经[3+2]环加成反应是构建五唑环的关键步骤。以对氨基苯酚、2-甲基-4-氨基苯酚和2,6-二甲基-4-氨基苯酚盐酸盐为原料,采用低温提取方法分离得到相应的盐酸重氮盐、硫酸重氮盐及四氟硼酸重氮盐固体,并通过光谱、质谱和扫描电子显微镜等确定其结构特征和形貌。热稳定性研究表明,随着苯环上羟基邻位上甲基取代个数的增加,所合成的重氮盐热稳定性越差,但四氟硼酸重氮盐的稳定性优于硫酸重氮盐和盐酸重氮盐。采用紫外光谱定性分析了不同重氮盐与叠氮化钠反应制备芳基的产率变化,结果表明,重氮盐的稳定性与其合成的芳基五唑收率呈反比关系,稳定性较差的3,5-二甲基-4-羟基苯基重氮盐酸盐合成的芳基五唑收率最好,当反应温度高于-30℃时芳基五唑的收率降低,所以合成芳基五唑温度应控制在-30℃及以下。The cycloaddition reaction between diazonium salts and diazo compounds is a key step for synthesis of aryl pentazole.Herein,a series of diazonium salts with different acid anion including Cl-,HSO_(4)^(-),and BF_(4)^(-),are prepared and separated via the low temperature extraction method by using 4-aminophenol,2-methyl-4-aminophenol,and 2,6-dimethyl-4-aminophenol hydrochloride as raw materials.Their structure and morphology are characterized by means of spectroscopy,mass spectrometry,and scanning electron microscopy.Thermal stability study indicates that the stability of synthesized diazonium salt becomes poorer with the increasing number of methyl substitution adjacent hydroxyl group on benzene ring.It is worth mentioning that tetrafluoroborate diazonium has much better stability than sulfate diazonium salt and diazonium hydrochloride.Subsequently,aryl pentazole is synthesized by reaction between sodium azide and different diazonium salts,and the yield rates are determined by means of UV-Vis spectrum.Results indicate that the yield of synthesized aryl pentazole has inverse relation with the stability of diazonium salts,where 3,5-dimethyl-4-hydroxyphenyl diazonium hydrochloride with lower stability delivers a high yield of aryl pentazole.It is also observed that the yield of aryl pentazoles declines when the reaction temperature is higher than-30℃.

关 键 词：多取代芳胺 重氮化盐 热稳定性 芳基五唑 

分 类 号：O62[理学—有机化学]