不同载体负载Mn（Salen）催化剂的微波固相法制备及其在苯乙烯环氧化反应中催化性能的比较
|
摘要
烯烃环氧化物在制药、塑料、香料、食物保存剂、生物农药等各个领域具有重要的应用价值。Mn(salen)络合物是非官能化烯烃环氧化反应中一种高效的催化剂，但由于存在催化剂与产品不易分离和催化剂难以重复使用等缺点，近年来，将Mn(salen)络合物固载或包合于无机或有机载体上制备多相催化剂受到广泛关注。然而，目前所报道的固载方法大都要求对载体表面进行有机官能化，普遍存在催化剂的制备过程复杂冗长等缺点。因此，研究一种更为简单的多相催化剂制备方法具有重要的学术意义和应用价值。
本文首次采用微波作用下的Mn(salen)络合物和载体之间的固态相互作用，通过离子交换或分子筛包合的方法，研究了不同载体负载Mn(salen)络合物的催化剂制备方法，用XRD、FT-IR、DR-UV-Vis和TG-DSC等研究手段对不同方法制备的催化剂进行了表征，以苯乙烯环氧化反应作为探针反应，考察了催化剂的不同制备方法和不同载体对苯乙烯环氧化反应的影响规律。
首先考察了不同salen配体和过渡金属离子制备的M(Salen)络合物在苯乙烯的环氧化反应中的催化性能，以乙二胺与水杨醛反应制备的Mn(Ⅲ)Salen催化剂在以H_2O_2为氧化剂，T=273 K，t=8h时，具有最好的催化活性和环氧化物选择性。
以MCM-41和HMS等介孔材料作为Mn(salen)络合物的载体，用微波固相法等不同方法制备了Mn(salen)／MCM-41和Mn(salen)／HMS催化剂。XRD结果表明MCM-41和HMS负载Mn(salen)络合物后仍具有典型的中孔特征，FT-IR对制备的催化剂表征结果表明负载的Mn(salen)均出现了Mn(salen)络合物的红外特征吸收带。考察了各种催化剂在苯乙烯环氧化反应中的催化性能，均表现出较好的催化活性和环氧化物选择性，但催化剂难以重复使用。
在MCM-41和HMS合成中通过掺铝对分子筛进行了改性，采用微波固相法制备了Mn(Salen)／Al-MCM-41和Mn(Salen)／Al-HMS催化
剂，并与常规制备方法进行了比较。FT一IR、DR UV一Vis和TG一SC
的表征结果表明，微波固相方法和常规方法均能成功地将Mn(salen)
络合物固载于介孔Al一MCM.41和AI.HMS分子筛中，且Mn(salen)
络合物与载体AI.MCM.41或AI.扭吐S之间存在较强的主客体相互作
用。在不同方法制备的催化剂中，以Salen配体、醋酸锰、氯化铿和
Al一CM.41或AI.I丑边S混合物经二氯甲烷溶剂浸渍后，再经微波辐
射制备的Mn(salen)/Al一MCM一41一护和Mn(SalenyAI.HMS一IP催化剂，
在苯乙烯环氧化反应中具有较高的催化活性和最好的环氧化物选择
性。此外，催化剂性能还与制备过程中的微波辐射时间有关。考察了
氧化剂种类和氧化剂量对苯乙烯环氧化反应的影响，以更加温和的
P址O为氧化剂可获得较高产率的环氧化物。以微波固相法制备的
N伍(Salen)/AI.HMS一护为催化剂，在苯乙烯环氧化反应中可重复使用。
相对常规的固载方法而言，采用微波固相法制备催化剂更加简单和省
时。
采用“瓶中造船”的方法，比较了微波固相法和常规方法将
腼(Salen)络合物包合于NaY分子筛中制备催化剂的不同方法。FT一IR
和DR UV一Vis的表征结果表明，微波固相合成法和常规合成法均能
成功地将Mh(Salen)络合物包合于NaY分子筛中。而采用分步浸渍微
波固相合成法制得的Mll(Salen)加ay一MWI样品在苯乙烯环氧化反应
中具有较高的催化活性和最好的环氧化物选择性，考察了溶剂和反应
温度对微波固相法制备的催化剂的性能影响规律，非极性溶剂中有利
于Mn(Salen)加ay催化剂中分子筛笼内的催化微环境形成，表现出更
好的催化活性和选择性，催化剂可重复使用。
The alkene epoxides find important application in Pharmaceuticals, plastics, perfumes, and pesticide. In this field, the use of Mn(salen) catalysts has received great attention in the last few years, given that they have shown to be useful in the epoxidation of non-functionalized olefins. Despite its interest, this method of epoxidation suffers from some drawbacks from a practical point of view. The high cost of the complex and the lack of recycling methods make it difficult for application of this system on a large scale. The encapsulation of salen complex using ship-in-bottle method and immobilization by ion exchange reaction are given more attention. But these methods are needed to react a functionlized ligand with reactive groups of organic and inorganic compounds. The procedure of synthesizing catalysts is complicated and essential to be carried out in organic solvent. It is important academic and practical values to simplify the procedure of heterogenized catalysts' preparation.
A novel method of preparation heterogeneous Mn(salen) catalysts by solid-state interaction between Mn(salen) complex and different supports under microwave irradiation is developed in this paper. The catalysts which prepared by different methods have been characterized by XRD, FTIR , DR UV-Vis, and TG-DSC techniques. The effects of catalysts prepared by different methods and the different supports on catalytic performances are investigated by the use of styrene epoxidation as probe reaction.
M (Salen) complex are synthesized by different metal ions and salen ligands. The complexes are characterized by FT-IR spectra. The catalytic performance is investigated by testing epoxidation of styrenc. It is found that the complex of Mn(Salen) which is synthesized by the ligand of
ethylenediamine with salicylaldehyde show the best catalytic activity and selectivity for epoxide among them when use H2O2 as oxidant at the temperature of 273 K for 8 h.
Mn(salen)/MCM-41 and Mn(salen)/HMS are prepared by solid-state-interaction under Microwave Irradiation. XRD spectra indicate that MCM-41 and HMS which supported Mn(salen) complex have typical mesoporous character. FT-IR spectra indicate that supported catalysts have characteristic IR bands of Mn(Salen) complex. The effect of catalyst preparation methods on the catalytic activity and selectivity of styrene epoxidation is also investigated. It is found that the catalyst of Mn(Salen)/MCM-41-IP or Mn(Salen)/HMS-IP showed high conversion of styrene and selectivity for phenyloxirane. But theses supported catalysts can not be reused.
Mn(Salen)/Al-MCM-41 and Mn(Salen)/Al-HMS catalysts are prepared by microwave irradiation (MWI) through host-guest interaction between Mn(Salen) complex and mesoporous Al-MCM-41 and Al-HMS. These catalysts are compared with the catalyst which prepared by conventional methods. FT-IR, DR UV-Vis, and TG-DSC results indicate that Mn(Salen) complex can be successfully immobilized on mesoporous materies which prepared by MWI method and conventional method. The strong host-guest interaction between Mn(Salen) complex and supports is found after Mn(Salen) complex immobilized on the supports. After impregnating the mixture of Salen ligand, manganese(II) acetate, lithium chloride, and the calcined Al-MCM-41 or Al-HMS with the solvent of dichloromethane, the mixture is irradiated by microwave. The catalysts prepared by this method are denoted as Mn(Salen)/Al-MCM-41-IP and Mn (Salen) /Al-HMS-IP. The effect of catalyst preparation methods on the catalytic activity and selectivity of styrene epoxidation is also investigated. It is
found that the catalyst of Mn(Salen)/Al-MCM-41-IP or Mn (Salen)/Al-HMS-IP show high conversion of styrene and the best selectivity for phenyloxirane.
The method of "ship-in-bottle" are used to encapsulate Mn(Salen) complex into NaY zeolite by microwave irradiation through solid-state interaction and conventional method. FT-IR and DR UV-Vis spectra indicate that Mn(Salen) complex can be successfully encapsulated into NaY cages which prepared by MWI method and or
本文首次采用微波作用下的Mn(salen)络合物和载体之间的固态相互作用，通过离子交换或分子筛包合的方法，研究了不同载体负载Mn(salen)络合物的催化剂制备方法，用XRD、FT-IR、DR-UV-Vis和TG-DSC等研究手段对不同方法制备的催化剂进行了表征，以苯乙烯环氧化反应作为探针反应，考察了催化剂的不同制备方法和不同载体对苯乙烯环氧化反应的影响规律。
首先考察了不同salen配体和过渡金属离子制备的M(Salen)络合物在苯乙烯的环氧化反应中的催化性能，以乙二胺与水杨醛反应制备的Mn(Ⅲ)Salen催化剂在以H_2O_2为氧化剂，T=273 K，t=8h时，具有最好的催化活性和环氧化物选择性。
以MCM-41和HMS等介孔材料作为Mn(salen)络合物的载体，用微波固相法等不同方法制备了Mn(salen)／MCM-41和Mn(salen)／HMS催化剂。XRD结果表明MCM-41和HMS负载Mn(salen)络合物后仍具有典型的中孔特征，FT-IR对制备的催化剂表征结果表明负载的Mn(salen)均出现了Mn(salen)络合物的红外特征吸收带。考察了各种催化剂在苯乙烯环氧化反应中的催化性能，均表现出较好的催化活性和环氧化物选择性，但催化剂难以重复使用。
在MCM-41和HMS合成中通过掺铝对分子筛进行了改性，采用微波固相法制备了Mn(Salen)／Al-MCM-41和Mn(Salen)／Al-HMS催化
剂，并与常规制备方法进行了比较。FT一IR、DR UV一Vis和TG一SC
的表征结果表明，微波固相方法和常规方法均能成功地将Mn(salen)
络合物固载于介孔Al一MCM.41和AI.HMS分子筛中，且Mn(salen)
络合物与载体AI.MCM.41或AI.扭吐S之间存在较强的主客体相互作
用。在不同方法制备的催化剂中，以Salen配体、醋酸锰、氯化铿和
Al一CM.41或AI.I丑边S混合物经二氯甲烷溶剂浸渍后，再经微波辐
射制备的Mn(salen)/Al一MCM一41一护和Mn(SalenyAI.HMS一IP催化剂，
在苯乙烯环氧化反应中具有较高的催化活性和最好的环氧化物选择
性。此外，催化剂性能还与制备过程中的微波辐射时间有关。考察了
氧化剂种类和氧化剂量对苯乙烯环氧化反应的影响，以更加温和的
P址O为氧化剂可获得较高产率的环氧化物。以微波固相法制备的
N伍(Salen)/AI.HMS一护为催化剂，在苯乙烯环氧化反应中可重复使用。
相对常规的固载方法而言，采用微波固相法制备催化剂更加简单和省
时。
采用“瓶中造船”的方法，比较了微波固相法和常规方法将
腼(Salen)络合物包合于NaY分子筛中制备催化剂的不同方法。FT一IR
和DR UV一Vis的表征结果表明，微波固相合成法和常规合成法均能
成功地将Mh(Salen)络合物包合于NaY分子筛中。而采用分步浸渍微
波固相合成法制得的Mll(Salen)加ay一MWI样品在苯乙烯环氧化反应
中具有较高的催化活性和最好的环氧化物选择性，考察了溶剂和反应
温度对微波固相法制备的催化剂的性能影响规律，非极性溶剂中有利
于Mn(Salen)加ay催化剂中分子筛笼内的催化微环境形成，表现出更
好的催化活性和选择性，催化剂可重复使用。
The alkene epoxides find important application in Pharmaceuticals, plastics, perfumes, and pesticide. In this field, the use of Mn(salen) catalysts has received great attention in the last few years, given that they have shown to be useful in the epoxidation of non-functionalized olefins. Despite its interest, this method of epoxidation suffers from some drawbacks from a practical point of view. The high cost of the complex and the lack of recycling methods make it difficult for application of this system on a large scale. The encapsulation of salen complex using ship-in-bottle method and immobilization by ion exchange reaction are given more attention. But these methods are needed to react a functionlized ligand with reactive groups of organic and inorganic compounds. The procedure of synthesizing catalysts is complicated and essential to be carried out in organic solvent. It is important academic and practical values to simplify the procedure of heterogenized catalysts' preparation.
A novel method of preparation heterogeneous Mn(salen) catalysts by solid-state interaction between Mn(salen) complex and different supports under microwave irradiation is developed in this paper. The catalysts which prepared by different methods have been characterized by XRD, FTIR , DR UV-Vis, and TG-DSC techniques. The effects of catalysts prepared by different methods and the different supports on catalytic performances are investigated by the use of styrene epoxidation as probe reaction.
M (Salen) complex are synthesized by different metal ions and salen ligands. The complexes are characterized by FT-IR spectra. The catalytic performance is investigated by testing epoxidation of styrenc. It is found that the complex of Mn(Salen) which is synthesized by the ligand of
ethylenediamine with salicylaldehyde show the best catalytic activity and selectivity for epoxide among them when use H2O2 as oxidant at the temperature of 273 K for 8 h.
Mn(salen)/MCM-41 and Mn(salen)/HMS are prepared by solid-state-interaction under Microwave Irradiation. XRD spectra indicate that MCM-41 and HMS which supported Mn(salen) complex have typical mesoporous character. FT-IR spectra indicate that supported catalysts have characteristic IR bands of Mn(Salen) complex. The effect of catalyst preparation methods on the catalytic activity and selectivity of styrene epoxidation is also investigated. It is found that the catalyst of Mn(Salen)/MCM-41-IP or Mn(Salen)/HMS-IP showed high conversion of styrene and selectivity for phenyloxirane. But theses supported catalysts can not be reused.
Mn(Salen)/Al-MCM-41 and Mn(Salen)/Al-HMS catalysts are prepared by microwave irradiation (MWI) through host-guest interaction between Mn(Salen) complex and mesoporous Al-MCM-41 and Al-HMS. These catalysts are compared with the catalyst which prepared by conventional methods. FT-IR, DR UV-Vis, and TG-DSC results indicate that Mn(Salen) complex can be successfully immobilized on mesoporous materies which prepared by MWI method and conventional method. The strong host-guest interaction between Mn(Salen) complex and supports is found after Mn(Salen) complex immobilized on the supports. After impregnating the mixture of Salen ligand, manganese(II) acetate, lithium chloride, and the calcined Al-MCM-41 or Al-HMS with the solvent of dichloromethane, the mixture is irradiated by microwave. The catalysts prepared by this method are denoted as Mn(Salen)/Al-MCM-41-IP and Mn (Salen) /Al-HMS-IP. The effect of catalyst preparation methods on the catalytic activity and selectivity of styrene epoxidation is also investigated. It is
found that the catalyst of Mn(Salen)/Al-MCM-41-IP or Mn (Salen)/Al-HMS-IP show high conversion of styrene and the best selectivity for phenyloxirane.
The method of "ship-in-bottle" are used to encapsulate Mn(Salen) complex into NaY zeolite by microwave irradiation through solid-state interaction and conventional method. FT-IR and DR UV-Vis spectra indicate that Mn(Salen) complex can be successfully encapsulated into NaY cages which prepared by MWI method and or
引文
[1] K. Srinivasan, P. Michaud, J. K. Kochi. Epoxidation of olefins with cationic (salen)Mn~Ⅲ complexes -the modulation of catalytic activity by substituents. J. Am. Chem. Soc., 1986, 108:2309
[2] K. Nakajima, M. Kojima, J. Fujita. Kinetic studies of epimerization of Cobalt(Ⅲ) complexes by means of high-performance liquid chromatography on a cation exchanger derived from TSK gel G3000PW. Chem. Lett., 1986: 1483
[3] Y. Naruta, F. Tani, K. Maruyama. High oxygen-evolving activity of rigidly linked manganese(Ⅲ) porphyrin dimmers-functional model of manganese catalyse. Chem. Lett., 1989:1269
[4] W. Zhang, J. L. Loebach, S. R. Wilson, E. N. Jacobsen. Enantioselective epoxidation of unfunctionalized olefins catalyzed by (salen) manganese complexes, J. Am. Chem. Soc., 1990, 112:2801
[5] R. Irie, K. Noda, Y. Ito, N. Matsumoto, T. Katsuki. Enantioselective epoxidation of unfunctionalized olefins using chiral(salen) manganese(Ⅲ) complexes. Tetrahedron. Lett., 1990, 31: 7345
[6] E. N. Jacobsen, W. Zhang, A. R. Muci, J. R. Ecker, L. Deng. Highly enantioselective epoxidation catalysts derived from 1,2-diaminocyclohexane. J. Am. Chem. Soc., 1991, 113: 7063
[7] P. R. Fleming, K. B. Sharpless. Selective transformations of threo-2,3-dihydroxy esters. J. Org. Chem., 1991, 56:2869
[8] H. Sasuki, R. Irie, T. Hamada, K. Suzuki, T. Katsuki. Rational design of Mn-salen catalyst(2):highly enantioselective epoxidation of conjugated cis-olefins. Tetrahedron, 1994, 50:11827
[9] Y. N. Ito, T. Katsuki. What is the origin of highly asymmetric induction by a chiral (salen)manganese(Ⅲ) complex-design of a conformationally fixed complex and its application to asymmetric epoxidation of 2,2-dimethylchromenes. Tetrahedron. Lett., 1998, 39:4325
[10] L. Deng, E. N. Jacobsen. A practical highly enantioselective synthesis of the Taxol Side Chain via asymmetric catalysis. J. Org. Chem., 1992, 57:4320
[11] J. F. Larrow, E. N. Jacobsen. A practical method for the large-scale preparation of [N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminatl(2-)] manganese(Ⅲ) chloride-a highly enantioselective epoxidation catalyst. J. Org. Chem., 1994, 59:1939
[12] J. T. Groves, R. S. Myers. Catalytic asymmetric epoxidations with chiral iron porphyrins. J Am. Chem. Soc., 1983, 105:5791
[13] J. P. Collman, X. Zhang, V. J. Lee, E. S. Uffelman, J. I. Brauman. Regioselective and enantioselective epoxidation catalyzed by metalloporphyrins. Science, 1993, 261:1404
[14] S. Chang, J. M. Galvin, E. N. Jacobsen. Effect of chiral quaternary ammonium salts (salen) Mn-catalyzed epoxidation of cis-olefins.a highly enantioselective, catalytic route to trans-epoxides. J. Am. Chem. Soc., 1994, 116:6937
[15] F. Minutolo, D. Pini, P. Salvadori. Polymer-bound chiral(salen) Mn(Ⅲ) complex as heterogeneous catalyst in rapid and clean enantioselective epoxidation of unfunctionalized olefins. Tetrahedron: Asymmetry, 1996, 7: 2293
[16] L. Canali, E. Cowan, H. Deleuze, C. L. Gibson, D. C. Sherrington. Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts. Chem. Commun., 1998, 23:2561
[17] X. Q. Yao, H. L. Chen, W. R. Lue, G. Z. Pan, X. Q. Hu, Z. Zheng. Enantioselective epoxidation of olefins catalyzed by two novel chiral poly-salen-Mn(Ⅲ) complexes. Tetrahedron. Lett., 2000, 41:10267
[18] K. B. Jansen, J. Laquiere, J. Dehaen, R. F. Parton, J. F. J. Wankelecom, P. A. Jacobs. A dimeric form of Jacobsen's catalyst for improved retention in a polydimethylsiloxane membrane. Tetrahedron:Asymmetry, 1997, 8: 3481
[19] A. Corma, A. Fuerte, M. Iglesias, F. Sanchez. Preparaton of new chiral dioxomolybdenum complexes heterogenized on modified USY-zeolite-efficient catalysts for catalysts for selective epoxidation of allylic alcohols.J. Mol. Catal. A: Chem, 1996, 107:225
[20] G. J. Kim, S. H. Kim. Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene. Catal. Lett., 1999, 57:139
[21] L. Barloy, P. Battioni, D. Mansuy. Manganese porphyrins supported on montmorillonite as hydrocarbon monooxygenation catalysts:particular efficacy for linear alkane hydroxylation, J. Chem. Soc. Chem. Commun., 1990: 1365
[22] S. B. Ogunwumi, T. Bein. Intrazeolite assembly of a chiral manganese salen epoxidation catalyst. J. Chem. Soc. Chem. Commun., 1997:901
[23] M. J. Sabater, A. Corma, A. Domenech, V. Formes. Chiral salen manganese complex encapsulated within zeolite Y: a heterogeneous enantioselective catalyst for the epoxidation fo alkenes. J. Chem. Soc. Chem. Commun., 1997: 1285
[24] N. Henon. A cobalt oxygen carrier in zellite Y-a molecular of "ship in a bottle", Inorg. Chem., 1986, 25:4714
[25] C. Bowers, P. Dutta. Olefin oxidation by zeolite-encapsulated manganese(salen)~+ emolexes under ambient conditions. J. Catal., 1990, 122:271
[26] P. V. Saji, R. Chandra, R. Paul. Zeolite-encapsulated manganese(Ⅲ)salen complexes. J. Mol Cat. A., 1998, 135:295
[27] D. Pini, A. Mandoli, S. Orlandi, P. Saivadori. Heterogeneous transition metal catalysts.enantioselective hydrogenatin and dihydroxylation of the carbon double bond. Tetrahedron:Asymmetry, 1999, 10:3883
[28] G. J. Kim, J. H. Shin. The catalytic activity of new chiral salen complexes immobilized on MCM-41 by multi-step grafting in the asymmetric
epoxidation. Tetrahedron. Lett., 1999, 40:6827
[29] T. S. Reger, K. D. Janda. Polymer-supported (salen)Mn catalysts for asymmetric epoxidation:a comparison between soluble and insoluble matrices. J. Am. Chem. Soc., 2000, 122:6929
[30] P. Piaggio, C. Langham, E Mcmom, D. Bethel, E C. Bulman-Page, F. E. Hancock, C. Sly, G. J. Hutching. Catalytic asymmetric epoxidation of stilbene using a chiral salon complex immobilized in Mn-exchanged Al-MCM-41. J. Chem. Soc. Perkin Trans., 2000, 22:143
[31] H. U. Blaser, B. Pugin. Chiral Reactions in Heterogeneous Catalysis (eds.Janners G.Dubois V). New York: Plenum Press, 1995:33
[32] B. M. Choudary, N. Sreenivasa Chowdari, M. Lakshmi Kantam, P Lakshmi Santhi. Silica Gel Anchored Chiral Mn(Ⅲ)Salen Complexes for Enantioselectivo Epoxidation of Unfunctionalised Olefins. Catal. Lett., 2001, 76:213
[33] B. M. Choudary, M. L. Kantam, B. Bharathi, E Sreekanth, F. Figueras. Epoxidatins of olefins catalysed by new Mn(Ⅱ) salen immobilized mosoporous materials. J. Mol. Catal. A., 2000, 159:417
[34] J. M. Fruile, J. I. Garcia, J. Massam, J. A. Mayoral. Clay-supported non-chiral and chiral Mn(salen) complexes as catalysts for olefin epoxidation. J. Mol. Cat. A., 1998, 136:47
[35] P. Sutra, D. Brunel. Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts. Chem. Commun., 1996, 21:2485
[36] G. Pozzi, E Cinato, F. Montanari. Efficient aerobic epoxidation of alkenes in perfluorinated solvents catalysed by chairal(salen)Mn complexes. J. Chem. Soc. Chem. Commun., 1998:877
[37] W. Zhang, E. N. Jacobsen. Asymmetric olefin epoxidation with sodium hypochlorite catalyzed by easily prepared chiral Mn(Ⅲ) salen complexes. J. Org. Chem., 1991, 56:2296
[38] P. Pietikaeinen. Convenient asymmetric (salen)Mn(Ⅲ)-catalyzed epoxidatin
of unfunctionalized alkenes with h7ydrogen peroxide using carboxylate salt cocatalysts. Tetrahedron, 1998, 54:4319
[39] N. Hosoya, R. Irie, T. Katsuki. Construction of new optically active(salen)manganese(Ⅲ) complexes ans their application to asymmetric epoxidation of styrene derivatives. Synlett, 1993: 261
[40] N. Hosoya, H. Akira, R. Irie, I. Sasaki, T. Katsuki. Rational design of Mn-salen epoxidation catalysts:preliminary results. Tetrahedron, 1994, 50: 4311
[41] H. Fu, G. C. Look, W. Zhang, E. N. Jacobsen, C. H. Wong. Mechanistic study of a synthetically useful monooxygenase model using the hypersensitive probe trans-2-phenyl-1-vinylcyclopropane. J. Org. Chem., 1991,.56:6497
[42] T. Hamada, T. Fukuda, H. Imanishi, T. Katsuki. Mechanism of one oxygen atom transfer from oxo (salen)manganese(Ⅴ) complex to olefins. Tetrahedron, 1996, 52:515
[43] T. Hamada, R. Irie, T. Ksatsuki. How does chiral OXO(salen) manganese(Ⅴ) complex.discrtiminate the enantioface of simple olefins?scope and limitation of salen-catalyzed epoxidation. Synlett, 1994:479
[44] 银董红、尹笃林、蒋汉瀛．微波辐射改性ZnCl_2-HY分子筛催化剂 □．在苯甲醚乙酰化反应中的催化性能．化学通报，1997，8：55
[45] S-E. Park, D-S. Kim, J-S. Chang, W-Y. Kim. Synthesis of MCM-41 using microwave heating with ethylene glycol. Catalysis. Today., 1998,44: 1-4: 301
[46] 张扬健、赵杉林、孙桂大、王振龙．W-MCM-48中孔分子筛的微波合成与表征．催化学报，2000，2l：4345
[47] D. H. Yin, D. L. Yin, The dispersion and solid-state ion exchange of ZnCl_2 onto the surface of NaY zeolite using microwave irradiation, Microporous and Mesoporous Materials, 1998, 24:123
[48] J. F. Li, D. H. Yin, D. L. Yin, Z. H. Fu, Q. H. Li, ZnCl_2 supported on NaY
zeolite by solid-state interaction under microwave irradiation and used as heterogeneous catalysts for high regioselective Diels-Alder reaction of myrcene and acrolein, Journal of Molecular Catalysis A: Chemical, 2003, 209/1-2 : 171-177
[49] D. H. Yin, D. L. Yin, Z. H. Fu, Q. H. Li, The Regioselectivity of Friedel-Crafts acylation of Anisole and acetyl chloride using ZnCl_2/HY zeolite modified by microwave irradiation as catalysts, 分子催化, 1998, 12: 401
[50] 银董红，尹笃林，伏再辉，李谦和．分子筛表面酸性对微波固相法制备的ZnCl_2／HY催化剂的影响．催化学报，2002，23(6)：567
[51] 银董红，尹笃林，微波辐射促进ZnCl_2与Y分子筛固相反应的研究，物理化学学报，1998，14：448
[2] K. Nakajima, M. Kojima, J. Fujita. Kinetic studies of epimerization of Cobalt(Ⅲ) complexes by means of high-performance liquid chromatography on a cation exchanger derived from TSK gel G3000PW. Chem. Lett., 1986: 1483
[3] Y. Naruta, F. Tani, K. Maruyama. High oxygen-evolving activity of rigidly linked manganese(Ⅲ) porphyrin dimmers-functional model of manganese catalyse. Chem. Lett., 1989:1269
[4] W. Zhang, J. L. Loebach, S. R. Wilson, E. N. Jacobsen. Enantioselective epoxidation of unfunctionalized olefins catalyzed by (salen) manganese complexes, J. Am. Chem. Soc., 1990, 112:2801
[5] R. Irie, K. Noda, Y. Ito, N. Matsumoto, T. Katsuki. Enantioselective epoxidation of unfunctionalized olefins using chiral(salen) manganese(Ⅲ) complexes. Tetrahedron. Lett., 1990, 31: 7345
[6] E. N. Jacobsen, W. Zhang, A. R. Muci, J. R. Ecker, L. Deng. Highly enantioselective epoxidation catalysts derived from 1,2-diaminocyclohexane. J. Am. Chem. Soc., 1991, 113: 7063
[7] P. R. Fleming, K. B. Sharpless. Selective transformations of threo-2,3-dihydroxy esters. J. Org. Chem., 1991, 56:2869
[8] H. Sasuki, R. Irie, T. Hamada, K. Suzuki, T. Katsuki. Rational design of Mn-salen catalyst(2):highly enantioselective epoxidation of conjugated cis-olefins. Tetrahedron, 1994, 50:11827
[9] Y. N. Ito, T. Katsuki. What is the origin of highly asymmetric induction by a chiral (salen)manganese(Ⅲ) complex-design of a conformationally fixed complex and its application to asymmetric epoxidation of 2,2-dimethylchromenes. Tetrahedron. Lett., 1998, 39:4325
[10] L. Deng, E. N. Jacobsen. A practical highly enantioselective synthesis of the Taxol Side Chain via asymmetric catalysis. J. Org. Chem., 1992, 57:4320
[11] J. F. Larrow, E. N. Jacobsen. A practical method for the large-scale preparation of [N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminatl(2-)] manganese(Ⅲ) chloride-a highly enantioselective epoxidation catalyst. J. Org. Chem., 1994, 59:1939
[12] J. T. Groves, R. S. Myers. Catalytic asymmetric epoxidations with chiral iron porphyrins. J Am. Chem. Soc., 1983, 105:5791
[13] J. P. Collman, X. Zhang, V. J. Lee, E. S. Uffelman, J. I. Brauman. Regioselective and enantioselective epoxidation catalyzed by metalloporphyrins. Science, 1993, 261:1404
[14] S. Chang, J. M. Galvin, E. N. Jacobsen. Effect of chiral quaternary ammonium salts (salen) Mn-catalyzed epoxidation of cis-olefins.a highly enantioselective, catalytic route to trans-epoxides. J. Am. Chem. Soc., 1994, 116:6937
[15] F. Minutolo, D. Pini, P. Salvadori. Polymer-bound chiral(salen) Mn(Ⅲ) complex as heterogeneous catalyst in rapid and clean enantioselective epoxidation of unfunctionalized olefins. Tetrahedron: Asymmetry, 1996, 7: 2293
[16] L. Canali, E. Cowan, H. Deleuze, C. L. Gibson, D. C. Sherrington. Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts. Chem. Commun., 1998, 23:2561
[17] X. Q. Yao, H. L. Chen, W. R. Lue, G. Z. Pan, X. Q. Hu, Z. Zheng. Enantioselective epoxidation of olefins catalyzed by two novel chiral poly-salen-Mn(Ⅲ) complexes. Tetrahedron. Lett., 2000, 41:10267
[18] K. B. Jansen, J. Laquiere, J. Dehaen, R. F. Parton, J. F. J. Wankelecom, P. A. Jacobs. A dimeric form of Jacobsen's catalyst for improved retention in a polydimethylsiloxane membrane. Tetrahedron:Asymmetry, 1997, 8: 3481
[19] A. Corma, A. Fuerte, M. Iglesias, F. Sanchez. Preparaton of new chiral dioxomolybdenum complexes heterogenized on modified USY-zeolite-efficient catalysts for catalysts for selective epoxidation of allylic alcohols.J. Mol. Catal. A: Chem, 1996, 107:225
[20] G. J. Kim, S. H. Kim. Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene. Catal. Lett., 1999, 57:139
[21] L. Barloy, P. Battioni, D. Mansuy. Manganese porphyrins supported on montmorillonite as hydrocarbon monooxygenation catalysts:particular efficacy for linear alkane hydroxylation, J. Chem. Soc. Chem. Commun., 1990: 1365
[22] S. B. Ogunwumi, T. Bein. Intrazeolite assembly of a chiral manganese salen epoxidation catalyst. J. Chem. Soc. Chem. Commun., 1997:901
[23] M. J. Sabater, A. Corma, A. Domenech, V. Formes. Chiral salen manganese complex encapsulated within zeolite Y: a heterogeneous enantioselective catalyst for the epoxidation fo alkenes. J. Chem. Soc. Chem. Commun., 1997: 1285
[24] N. Henon. A cobalt oxygen carrier in zellite Y-a molecular of "ship in a bottle", Inorg. Chem., 1986, 25:4714
[25] C. Bowers, P. Dutta. Olefin oxidation by zeolite-encapsulated manganese(salen)~+ emolexes under ambient conditions. J. Catal., 1990, 122:271
[26] P. V. Saji, R. Chandra, R. Paul. Zeolite-encapsulated manganese(Ⅲ)salen complexes. J. Mol Cat. A., 1998, 135:295
[27] D. Pini, A. Mandoli, S. Orlandi, P. Saivadori. Heterogeneous transition metal catalysts.enantioselective hydrogenatin and dihydroxylation of the carbon double bond. Tetrahedron:Asymmetry, 1999, 10:3883
[28] G. J. Kim, J. H. Shin. The catalytic activity of new chiral salen complexes immobilized on MCM-41 by multi-step grafting in the asymmetric
epoxidation. Tetrahedron. Lett., 1999, 40:6827
[29] T. S. Reger, K. D. Janda. Polymer-supported (salen)Mn catalysts for asymmetric epoxidation:a comparison between soluble and insoluble matrices. J. Am. Chem. Soc., 2000, 122:6929
[30] P. Piaggio, C. Langham, E Mcmom, D. Bethel, E C. Bulman-Page, F. E. Hancock, C. Sly, G. J. Hutching. Catalytic asymmetric epoxidation of stilbene using a chiral salon complex immobilized in Mn-exchanged Al-MCM-41. J. Chem. Soc. Perkin Trans., 2000, 22:143
[31] H. U. Blaser, B. Pugin. Chiral Reactions in Heterogeneous Catalysis (eds.Janners G.Dubois V). New York: Plenum Press, 1995:33
[32] B. M. Choudary, N. Sreenivasa Chowdari, M. Lakshmi Kantam, P Lakshmi Santhi. Silica Gel Anchored Chiral Mn(Ⅲ)Salen Complexes for Enantioselectivo Epoxidation of Unfunctionalised Olefins. Catal. Lett., 2001, 76:213
[33] B. M. Choudary, M. L. Kantam, B. Bharathi, E Sreekanth, F. Figueras. Epoxidatins of olefins catalysed by new Mn(Ⅱ) salen immobilized mosoporous materials. J. Mol. Catal. A., 2000, 159:417
[34] J. M. Fruile, J. I. Garcia, J. Massam, J. A. Mayoral. Clay-supported non-chiral and chiral Mn(salen) complexes as catalysts for olefin epoxidation. J. Mol. Cat. A., 1998, 136:47
[35] P. Sutra, D. Brunel. Remarkable matrix effect in polymer-supported Jacobsen's alkene epoxidation catalysts. Chem. Commun., 1996, 21:2485
[36] G. Pozzi, E Cinato, F. Montanari. Efficient aerobic epoxidation of alkenes in perfluorinated solvents catalysed by chairal(salen)Mn complexes. J. Chem. Soc. Chem. Commun., 1998:877
[37] W. Zhang, E. N. Jacobsen. Asymmetric olefin epoxidation with sodium hypochlorite catalyzed by easily prepared chiral Mn(Ⅲ) salen complexes. J. Org. Chem., 1991, 56:2296
[38] P. Pietikaeinen. Convenient asymmetric (salen)Mn(Ⅲ)-catalyzed epoxidatin
of unfunctionalized alkenes with h7ydrogen peroxide using carboxylate salt cocatalysts. Tetrahedron, 1998, 54:4319
[39] N. Hosoya, R. Irie, T. Katsuki. Construction of new optically active(salen)manganese(Ⅲ) complexes ans their application to asymmetric epoxidation of styrene derivatives. Synlett, 1993: 261
[40] N. Hosoya, H. Akira, R. Irie, I. Sasaki, T. Katsuki. Rational design of Mn-salen epoxidation catalysts:preliminary results. Tetrahedron, 1994, 50: 4311
[41] H. Fu, G. C. Look, W. Zhang, E. N. Jacobsen, C. H. Wong. Mechanistic study of a synthetically useful monooxygenase model using the hypersensitive probe trans-2-phenyl-1-vinylcyclopropane. J. Org. Chem., 1991,.56:6497
[42] T. Hamada, T. Fukuda, H. Imanishi, T. Katsuki. Mechanism of one oxygen atom transfer from oxo (salen)manganese(Ⅴ) complex to olefins. Tetrahedron, 1996, 52:515
[43] T. Hamada, R. Irie, T. Ksatsuki. How does chiral OXO(salen) manganese(Ⅴ) complex.discrtiminate the enantioface of simple olefins?scope and limitation of salen-catalyzed epoxidation. Synlett, 1994:479
[44] 银董红、尹笃林、蒋汉瀛．微波辐射改性ZnCl_2-HY分子筛催化剂 □．在苯甲醚乙酰化反应中的催化性能．化学通报，1997，8：55
[45] S-E. Park, D-S. Kim, J-S. Chang, W-Y. Kim. Synthesis of MCM-41 using microwave heating with ethylene glycol. Catalysis. Today., 1998,44: 1-4: 301
[46] 张扬健、赵杉林、孙桂大、王振龙．W-MCM-48中孔分子筛的微波合成与表征．催化学报，2000，2l：4345
[47] D. H. Yin, D. L. Yin, The dispersion and solid-state ion exchange of ZnCl_2 onto the surface of NaY zeolite using microwave irradiation, Microporous and Mesoporous Materials, 1998, 24:123
[48] J. F. Li, D. H. Yin, D. L. Yin, Z. H. Fu, Q. H. Li, ZnCl_2 supported on NaY
zeolite by solid-state interaction under microwave irradiation and used as heterogeneous catalysts for high regioselective Diels-Alder reaction of myrcene and acrolein, Journal of Molecular Catalysis A: Chemical, 2003, 209/1-2 : 171-177
[49] D. H. Yin, D. L. Yin, Z. H. Fu, Q. H. Li, The Regioselectivity of Friedel-Crafts acylation of Anisole and acetyl chloride using ZnCl_2/HY zeolite modified by microwave irradiation as catalysts, 分子催化, 1998, 12: 401
[50] 银董红，尹笃林，伏再辉，李谦和．分子筛表面酸性对微波固相法制备的ZnCl_2／HY催化剂的影响．催化学报，2002，23(6)：567
[51] 银董红，尹笃林，微波辐射促进ZnCl_2与Y分子筛固相反应的研究，物理化学学报，1998，14：448