四硝基二苯并-1,3a,4,6a-四氮杂戊搭烯的合成工艺改进

Improvement of tetranitrodibenzo-1,3a,4,6a-tetrazapentalene synthetic processes

为了改进四硝基二苯并-1,3a,4,6a-四氮杂戊搭烯(TACOT)的合成工艺,以邻苯二胺为原料,通过氧化、重氮化-取代、合环和硝化四步得到了TACOT,总收率为45.9%,采用红外光谱、核磁共振和元素分析等进行结构表征;探讨不同脱色剂,脱色温度、脱色剂的用量及重氮化体系对氧化和重氮化-取代反应收率的影响;通过改变降温速率和搅拌转速等手段,制备出不同形貌的TACOT样品,采用差示扫描量热法(DSC)和热重量分析(TG)研究不同形貌TACOT样品的热性能。结果表明:在温度为35~40℃时,以硅胶作为脱色剂,邻苯二胺与硅胶质量比为1:3,使用硫酸/亚硝酸钠为重氮化体系时,反应收率最高为50.2%;调节转速为800 r×min-1,降温速率为0.5℃×min-1时可获得形状规则、表面光滑的TACOT样品,样品的DSC分解峰温为402.2℃,TG热失重起始温度为359.4℃。

The synthetic process of tetranitrodibenzo-1,3a,4,6a-tetrazapentalene(TACOT)was improved using O-phenylenedianmine as the primer reactant via oxidation,diazotization-substitution,cyclization and nitrification with a total yield of 45.9%,and its structure was characterized by NMR,IR and elemental analysis.The effects of different decolorizers,decolorizing temperatures,decolorizer dosages and diazotization systems on the yield of oxidation and diazotization-substitution were discussed,and different crystal morphology of TACOT were prepared by changing cooling rates and stirring speeds,thermal behaviors of the samples were studied by differential scanning calorimetry(DSC)and thermogravimetric analysis(TG).The results show that when silica gel is used as the decolorizer at 35-40℃,the mass ratio of O-phenylenedianmine and silica gel is 1:3,the highest yield is 50.16%when using H2SO4/NaNO2 as the diazotization system.TACOT with smooth surface and regular shape was prepared at 800 r×min-1 and cooling rate of 0.5℃×min-1,and the thermal decomposition peak of the sample in DSC and the starting point in TG were 402.2℃and 359.4℃,respectively.