有机化学 ›› 1996, Vol. 16 ›› Issue (6): 507-513. 上一篇    下一篇

研究论文

硫醚中碳硫键室温选择性断裂反应的研究

王磊;THOMAS K. GREEN   

  1. 淮北煤炭师范学院化学系;西肯德基大学化学系
  • 发布日期:1996-12-25

Study on the mechanism of selective carbon-sulfur bond cleavage in sulfide at room temperature

WANG LEI;THOMAS K. GREEN   

  • Published:1996-12-25

本文研究了在四氟硼酸银存在下, 硫醚与碘甲烷室温下发生碳硫键选择性断裂反应。研究结果表明: 只有当二苄基硫醚的苯环对位连有强的供电子基团甲氧基时, 方可发生碳硫键的断裂。提出了一个离子型反应机理且碳硫键的断裂分三步完成。首先, 硫醚与甲基化试剂反应生成甲基锍盐; 继而, 此锍离子离解成由苄基碳正离子和硫醚组成的离子-偶极集合物; 最后, 甲基化试剂再进攻集合物中的硫醚, 从而导致碳硫键的断裂。

关键词: 其它基金, 硫醚, 碳硫键断裂, 选择性反应, 甲氧基, 断裂反应, 碘甲烷

The reaction of various dibenzylsulfides with excess methyl iodide in the presence of excess silver tetrafluoroborate at room temperature and the carbon-sulfur bond selective cleavage reaction in some case were studied. The results showed that only the benzyl group with p- methoxy substituent could undergo bond cleavage. The carbon-sulfur bond cleavage process might consist of three steps. The first, sulfide reacts with methylation agent to form methylsulfonium salt and the second, sulfonium ion undergoes dissociation to form an ion-dipole assemblage consisting of benzyl carbocation and sulfide. Finally, methylating agent attacks sulfide in assemblage to cleavage carbon- sulfur bond.

Key words: METHOXY GROUP, IODOMETHANE, SULFUR ETHER

中图分类号: