应用化学 ›› 2009, Vol. 26 ›› Issue (10): 1174-1179.

• 研究论文 • 上一篇    下一篇

手性salen Mn(Ⅲ)的制备及其对α-甲基苯乙烯不对称环氧化反应的催化

陈俊显,傅相锴,申红胜,涂小波,龚必伟,邹晓川   

  1. (西南大学化学化工学院应用化学研究所,重庆市应用化学重点实验室 重庆 400715)
  • 收稿日期:2008-10-09 修回日期:2008-12-22 出版日期:2009-10-10 发布日期:2009-10-10
  • 通讯作者: 傅相锴,男,教授,博士生导师; E-mail:fxk@swu.edu.cn; 研究方向:有机催化及功能材料
  • 基金资助:
    重庆市经委工业专项资金项目(2008-65)

Amination ZPS-IPPA axial coordination chiral Salen Mn (Ⅲ) Preparation of And a-methylstyrene asymmetric epoxidation reaction

CHEN Jun-Xian, FU Xiang-Kai, SHEN Hong-Sheng, TU Xiao-Bo, GONG Bi-Wei, ZOU Xiao-Chuan   

  1. (College of Chemistry and Chemical Engineering,Southwest University;Chongqing Key Laboratory of Applied Chemistry,Chongqing 400715)
  • Received:2008-10-09 Revised:2008-12-22 Published:2009-10-10 Online:2009-10-10

摘要:

本文以聚(苯乙烯-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)为载体,对该载体进行氯甲基化、胺化修饰后与手性Salen Mn(Ⅲ)轴向配位,合成了一种新的固载型手性Salen Mn(Ⅲ)催化剂,采用FTIR,DR UV-Vis,XPS,SEM,TEM,TG等手段对催化剂进行表征.以次氯酸钠和间氯过氧苯甲酸为氧化剂,考察了固载催化剂对a-甲基苯乙烯不对称环氧化反应的催化性能,结果表明,固载型催化剂的催化活性比相应均相催化剂略低,但对映体选择性明显提高.在NaClO/PPNO氧化剂体系中0 ℃反应24h,a-甲基苯乙烯环氧化物的转化率达68%,e.e.值达99%.循环使用8次后催化效果无明显降低.

关键词: 聚(苯乙烯-异丙烯膦酸)-磷酸氢锆, 手性Salen Mn( Ⅲ), 轴向固载催化剂, 不对称环氧化, a-甲基苯乙烯

Abstract:

Chiral Salen Mn(III) complex axial coordination immobilized on diamine or ployamines modified Zirconium poly (styrene-isopropenyl phosphonate)-phosphate(ZPS-IPPA),were prepared by a covalent grafting method. All the supported heterogeneous chiral Salen Mn(III) complexes prepared were characterized by FT-IR,diffusion reflection UV–vis,XPS,SEM,TEM and TG. The supported catalyst was applied to the enantioselective epoxidation of a-methylstyrene using NaClO and m-CPBA as oxidants. The result s confirmed that the activity of the supported catalyst was lower than that of the homogeneous chiral Salen Mn ( Ⅲ) . However,it s enantioselectivity was higher than that of the homogeneous one. A conversion of 68 % and ee of 99% of epoxide were obtained when a-methylstyrene was oxidized by NaClO for 24 h at 20 ℃ in the presence of the 4-PPNO. The catalysts were easily recovered by filtration and could be reused at least eight times with little loss of activity and enantioselectivity.

Key words: Zirconium poly (styrene-isopropenyl phosphonate)-phosphate, chiral Salen Mn ( Ⅲ), axial coordination supported catalyst, asymmetric epoxidation, a-methylstyrene

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