催化学报

催化学报 ›› 2007, Vol. 28 ›› Issue (1): 85-90.

• 研究论文 • 上一篇    下一篇

MCM-41负载手性Salen-Mn(Ⅲ)配合物的制备及其对不对称环氧化的催化性能

赵继全,张雅然,张月成   

  1. 河北工业大学化工学院, 天津 300130
  • 收稿日期:2007-01-25 出版日期:2007-01-25 发布日期:2010-08-28

Preparation of Chiral Salen-Mn(Ⅲ) Complex Supported on MCM-41 and Its Catalytic Properties for Enantioselective Epoxidation

ZHAO Jiquan*, ZHANG Yaran, ZHANG Yuecheng   

  1. School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, China
  • Received:2007-01-25 Online:2007-01-25 Published:2010-08-28

PDF

896

被引次数

38

摘要： 三乙氧基硅丙胺与介孔分子筛MCM-41表面的羟基在甲苯中回流反应得到氨丙基官能团化的MCM-41, 再利用氨基与Salen-Mn(Ⅲ)上的活性酯基生成酰胺键,将手性Salen-Mn(Ⅲ)配合物负载到MCM-41上,实现了手性均相催化剂的多相化. 分别利用FT-IR, DR UV-Vis, XRD, ICP和N2吸附等手段对负载型催化剂进行了表征. 结果表明,手性Salen-Mn(Ⅲ)配合物成功负载到MCM-41上,但MCM-41和手性Salen-Mn(Ⅲ)配合物固有的结构保持不变. 以次氯酸钠和间氯过氧苯甲酸为氧化剂,考察了负载型催化剂对1,2-二氢萘不对称环氧化反应的催化性能,结果表明,负载型催化剂的催化活性比相应均相催化剂的低,但对映体选择性有所提高. 在NaClO/PyNO氧化剂体系中20 ℃反应12 h, 1,2-二氢萘环氧化物的收率达45.9%, 对映体过量值为84.3%. 负载型催化剂在循环使用5次后Mn的流失达34%.

关键词: MCM-41分子筛, 手性Salen锰(Ⅲ)配合物, 负载型催化剂, 不对称环氧化, 二氢萘

Abstract: MCM-41 was functionalized with 3-aminopropyl groups by the reaction of hydroxyl groups on the MCM-41 surface with 3-aminopropyltriethoxysilane being refluxed in toluene. By employing the reaction of amino groups with active ester groups on the chiral Salen-Mn(Ⅲ) complex, the homogeneous chiral Salen-Mn(Ⅲ) complex was heterogenized. The supported catalyst was characterized by FT-IR, DR UV-Vis, XRD, ICP, and N2 adsorption. The results indicated that the complex was supported on MCM-41 and the native structure of MCM-41 was maintained. The supported catalyst was applied to the enantioselective epoxidation of 1,2-dihydronaphthalene using NaClO and m-chloroperbenzoic acid as oxidants. The results confirmed that the activity of the supported catalyst was lower than that of the homogeneous chiral Salen-Mn(Ⅲ). However, its enantioselectivity was higher than that of the homogeneous one. A yield of 45~9% and ee of 84~3% of epoxide were obtained when 1,2-dihydronaphthalene was oxidized by NaClO for 12 h at 20 ℃ in the presence of the pyridine nitrogen oxide. About 34% of manganese leaching was observed after the supported catalyst was run 5 times.

Key words: MCM-41 molecular sieve, chiral Salen-Mn(Ⅲ) complex, supported catalyst, enan