化学学报 ›› 2005, Vol. 63 ›› Issue (16): 1520-1524. 上一篇    下一篇

研究论文

固体催化剂用于二元醇分子内环化制内酯的研究

纪红兵*1,王乐夫1,佘远斌2   

  1. (1华南理工大学化工与能源学院广东省绿色化学产品技术重点实验室 广州 510640)
    (2北京工业大学绿色化学研究室 北京100022)
  • 投稿日期:2004-08-19 修回日期:2005-04-12 发布日期:2010-12-10
  • 通讯作者: 纪红兵

Intramolecular Cyclization of Diols into Lactone Using Solid Catalyst

JI Hong-Bing*1,WANG Le-Fu1,SHE Yuan-Bin2   

  1. (1 Guangdong Provincial Laboratory for Green Chemical Technology, School of Chemical and Energy Engineering,South China University of Technology, Guangzhou 510640)2 Laboratory of Green Chemistry, Beijing University of Technology, Beijing 100022)
  • Received:2004-08-19 Revised:2005-04-12 Published:2010-12-10
  • Contact: JI Hong-Bing

将钌改性的固体催化剂Ru-Co(OH)2-CeO2用于以分子氧作为氧化剂的二元醇的催化氧化内酯化反应中, 发现该催化剂具有很好的催化反应性能. 该催化剂可优先氧化伯碳上的羟基. 对反应机理的研究表明, 活性中心钌首先与反应物形成醇化物, 经β-氧化消除反应使得其中一羟基氧化, 经异构环化、氧化进一步脱氢形成内酯.

关键词: 二元醇, 内酯化, 固体催化剂

Ruthenium-modified solid catalyst Ru-Co(OH)2-CeO2 was applied to the lactonization of diols in the presence of molecular oxygen and achieved highly efficient catalytic performance. Hydroxyl group on the primary carbon could be preferentially oxidized to the corresponding carbonyl group. The research towards reaction mechanism presented that Ru-alkoxide intermediate could be formed from active ruthenium center and reactants, followed by oxidative β-hydride elimination, isomeric cyclization, and further oxidative dehydrogenation, and the product lactone could be obtained.

Key words: diol, lactonization, solid catalyst