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采用B3LYP、QCISD、MP2方法在6-311+G*基组水平上对HN3+NH2CN→5-AT的环加成反应进行了研究,用气相条件下的计算方法结合SCRF/PCM模型对四氯化碳、丙酮、二甲亚砜、水四种不同溶剂下的反应性能进行计算,探讨了溶剂对反应的影响。结果表明,溶剂的极性对反应的影响不明显,从热力学角度考虑:反应在二甲亚砜溶剂中的平衡常数最大,说明反应在二甲亚砜溶剂中最容易自发进行;从动力学角度考虑:反应在各种溶剂中的速率常数均小于其在气相条件下的速率常数,说明反应在气相条件下更具有动力学优势。300～350 K是该反应的适宜温度。
The cycloaddition reaction of HN3 + NH2CN → 5-AT at B3LYP, QCISD and MP2 levels was carried out on the 6-311 + G * basis set. The effects of tetrachloro Carbonization, acetone, dimethylsulfoxide and water. The effects of solvents on the reaction were discussed. The results show that the polarity of the solvent has no obvious effect on the reaction. From the thermodynamic point of view, the equilibrium constant of the reaction in the dimethyl sulfoxide solvent is the largest, indicating that the reaction is most likely to occur spontaneously in the dimethyl sulfoxide solvent. From the kinetic point of view It is considered that the rate constants of the reactions in various solvents are all less than those in the gas phase, indicating that the reaction is more kinetic at the gas phase. 300 ~ 350 K is the appropriate reaction temperature.