以聚(苯乙烯-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)为载体,通过对载体进行氯甲基化、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等测试技术对催化剂进行表征. 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α-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24 h,α-甲基苯乙烯环氧化反应的转化率达68%,对映选择性e.e.值达99%,循环使用8次后催化效果无明显降低.
Chiral Salen Mn(Ⅲ) complex was axially coordinated on diamine or polyamines modified Zirconium poly(styrene-isopropenyl phosphonate)-phosphates(ZPS-IPPA) 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 and TEM. The supported catalyst was applied to the enantioselective epoxidation of α-methylstyrene with NaClO and m-CPBA as oxidants. The results confirm that the activity of the supported catalyst was lower than that of the homogeneous chiral Salen Mn( Ⅲ). However, its enantioselecti-vity was higher than that of the homogeneous one. A conversion of 68% and an e.e. of 99% of epoxide were obtained when α-methylstyrene was oxidized by NaClO for 24 h at 0 ℃ in the presence of 4-PPNO. The catalysts were easily recovered by filtration and could be reused for at least eight times with little loss of activity and enantioselectivity.
参考文献
| [1] | Katsuki T.Adv Synth Catal[J],2002,344(2):131 |
| [2] | McGarrigle E M,Gilheany D G.Chem Rev[J],2005,105(5):1 563 |
| [3] | Bryliakov K P,Kholdeeva O A,Vanina M P,Talsi E P.J Mol Catal A:Chem[J],2002,178:47 |
| [4] | ZHANG Yan(张),YIN Dong-Hong(银董红),YANG Yi-Si(杨一思),HUANG Chun-Bao (黄春保).Chinese J Appl Chem(应用化学)[J],2006,23(6):646 |
| [5] | Song C E,Roh E J,Yu B M,Chi D Y,Kim S C,Lee K J.Chem Commun[J],2000,(7):615 |
| [6] | Sabater M J,Corma A,Domenech A,Fornes V,Garcia H.Chem Commun[J],1997,(14):1 285 |
| [7] | Piaggio P,Langham C,McMorn P,Bethell D,Bulman-Page P C,Hancock F E,Sly C,Hutchings J.J Chem Soc Perkin Trans[J],2000,2:143 |
| [8] | Fraile J M,Garcia J I,Massam J,Mayoral J A.J Mol Catal A:Chem[J],1998,136(1):47 |
| [9] | Gil S,Gonzalez R,Mestres R,Sanz V,Zapater A.React Funct Polym[J],1999,42(1):65 |
| [10] | FU Xiang-Kai(傅相锴),ZOU Kuang-Dong(邹矿东),FU Dan(富丹),GONG Rong-Feng(龚永锋).CN 200 610 095 053.1[P],2006 |
| [11] | Bai R F,FU X K,Bao H B,Ren W S.Catal Commun[J],2008,(9):1 58811 BAO He-Bin(包河彬),FU Xiang-Kai(傅相锴),BAI Ruo-Fei(白若飞),REN Wen-Shan(任文山),TU Xiao-Bo(涂小波).Chem J Chinese Univ(高等学校化学学报)[J],2008,29(5):927 |
| [12] | Bai R F,FU X K,Bao H B,Ren W S.Catal Commun[J],2008,(9):1 58811 BAO He-Bin(包河彬),FU Xiang-Kai(傅相锴),BAI Ruo-Fei(白若飞),REN Wen-Shan(任文山),TU Xiao-Bo(涂小波).Chem J Chinese Univ(高等学校化学学报)[J],2008,29(5):927 |
| [13] | Palncki M,Pospisil P J,Zhang W,Jacobsen E N.J Am Chem Soc[J],1994,116:9 333 |
| [14] | Silva A R,Figueiredo J L,Freire C,Castro B D,Castro B D.Microporous Mesoporous Mater[J],2004,68:83 |
| [15] | Tong J H,Zhang R,Li Z,Xia C G.J Mol Catal A:Chem[J],2006,249:47 |
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