2H-氮杂卓衍生物迁移反应的光谱学特征

氮杂卓化合物存在1H-,2H-,3H-和4H-共4个互变异构体,其中,2H-,3H-系统是最重要的。2H-氮杂卓母体化合物很不稳定,4位存在叔-丁基,并且环上含有丙硫基(PrS-)取代基的2H-氮杂卓,不仅发生H迁移,也能发生PrS-迁移,向较稳定的3H-氮杂卓异构化。以2,7-二甲氧基-4-甲基-2H-氮杂卓为原料,通过与Pr-SH的取代反应,合成7-甲氧基-4-甲基-2-PrS-2H-氮杂卓,并讨论分析产物的 迁移反应。通过IR、¹H NMR、¹³C NMR、MS检测表明,在室温条件下,4位存在甲基的2H-氮杂卓衍生物,选择性地发生 PrS-迁移,生成3H-氮杂卓,而且此异构化反应速度比叔-丁基存在时的情况更快。

Spectroscopy Studying on Derivatives 2H-azepine [1,5] PrS-migration Reaction

In many biologies and plants,the ring containing the nitrogen atom of azepine,which as biologically active substances, is an important group of organic compounds.There is tautomers between 1H-, 2H-, 3H- in azepine, among them 2H-, 3H- system are the most important.2H-azepine is unstable index compound, through H migration, the 3H-azepine isomerization is relatively stable.The existence of four tert-butyl and PrS- ring substituent containing the 2H-azepine,it not only can migrate to hydrogen atom, but also the movement of sulfur occurred,and 3H-azepine isomerization occurs.Regarding 2,7-dimethoxy-4-methyl-2H-azepine as raw materials, through the substitution reaction with propyl thiol, 7-methoxy-4-methyl-2-propylthio-2H-azepine was synthesized and migration reaction was analyzed.IR,1H NMR, 13C NMR, MS obervation showed that, at room temperature, the seletive PrS-migration base on 2H-azepine ring with 4-methyl 2H-azepine occures and 3H-arepine is established, wiche is faster than that with exitstence of tert-butyl.