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研究了温度、时间等因素对合成反应的影响,发现亚胺型杂卓4和烯胺型杂卓5分别为速度控制产物和平衡控制产物,并且实现了两种互变异构体的选择性合成.用核磁共振法研究了溶剂、酸碱度对4,5互变异构的影响,发现两种异构体在CD3OD,DMSO-d6,C6D6以及精制的CDCl3中比较稳定,在未精制的CDCl3中容易发生互变及开环反应,形成3,4,5的平衡混合物,并以4为主要组分.4,5在酸中不稳定,但在弱碱(吡啶)中能稳定存在.采用密度泛函理论方法在B3LYP/6-31G基组水平上对四组(八种)不同取代基的上述异构体进行了几何优化和计算.结果表明,烯胺型杂卓5比亚胺型杂卓4稳定,理论计算结果与实验结果基本一致.
The effects of temperature, time and other factors on the synthesis reaction were investigated. It was found that the imine-type tetrazoliums and the enamine-type tetrazoliums 5 were the rate control products and the equilibrium control products respectively, and the selectivity of the two tautomers was achieved The effects of solvents and pH on the tautomerism of 4 and 5 were investigated by NMR. The two isomers were found to be relatively stable in CD3OD, DMSO-d6, C6D6 and purified CD3, Prone to interconversion and ring opening reaction to form a balanced mixture of 3, 4 and 5, and 4 as the main component.4,5 instability in the acid, but stable in weak base (pyridine) can be used density Functional theory method was used to optimize and calculate the above isomers of four groups (eight kinds) of different substituents at B3LYP / 6-31G base group level. The results show that the enamine type 5-imine complex Zhuo 4 stable, the theoretical calculation results and experimental results are basically the same.