苯甲撑肼基二硫代甲酸甲酯热裂解的机理研究  

Pyrolysis Mechanism of S-Methyl Benzenylmethylenehydrazine Dithiocarboxylate

作　　者：边高峰[1] 蒋可志[1] 来国桥[1] 

机构地区：[1]杭州师范大学有机硅化学及材料技术教育部重点实验室,杭州310012

出　　处：《化学学报》2010年第23期2443-2448,共6页Acta Chimica Sinica

基　　金：杭州师范大学校级科研基金(No.2008XNM03);浙江省自然科学基金(No.Y4080380);浙江省钱江人才计划基金(No.2008R10018)资助项目

摘　　要：采用密度泛函理论对苯甲撑肼基二硫代甲酸甲酯的热裂解反应机理进行了研究.计算结果表明,烯胺碳上氢的六元环迁移途径比硫酰胺氢的四元环迁移途径更容易发生.同时,从机理上解释了苯环上的取代基电子效应对该类化合物裂解的影响,即吸电子基抑制裂解反应的发生,而推电子基则产生相反的效果.The mechanistic route for pyrolysis reaction of S-methyl benzenylmethylenehydrazine dithio-carboxylate has been investigated by density functional theory calculation.Calculation results show that the hydrogen on the eniminic group is kinetically more favorable to migrate to the thiocarbamine sulfur via a six-membered ring transition state TS-1b,than the thiocarbamine hydrogen via four-membered ring transition states in the pyrolytic elimination process.The electronic effect of the substituent on the phenyl group at para-position also affects the reaction by varying the calculated energy barrier.

关 键 词：热裂解反应 机理 密度泛函理论 电子效应 

分 类 号：O621.25[理学—有机化学]