将金属次卟啉二甲酯用作叔丁基过氧化氢(TBHP)氧化苯乙烯制苯甲醛的催化剂.考察了催化剂、氧化剂用量、反应温度、时间、溶剂和不同金属次卟啉二甲酯[M (DPDME)]对苯乙烯转化率及苯甲醛选择性的影响,初步探索了反应机理.结果表明,金属次卟啉二甲酯能够顺利地选择性催化氧化苯乙烯生成苯甲醛.以0.002 mmol锰次卟啉二甲酯[CIMn(DPDME)]为催化剂,0.4 mmol TBHP为氧化剂,1mmol苯乙烯为底物,5 mL CH3CN/H2O(体积比4∶1)为溶剂,反应温度75℃,常压反应20h,苯乙烯的转化率达到98.3％,苯甲醛的选择性为92.7％.
参考文献
| [1] | ZHOU Weiyou,HU Bingcheng,LIU Zuliang.Selective Oxidation of Cyclohexane Catalyzed by Metallo-Deuteroporphyrins in Homogeneous Solution[J].Chinese J Appl Chem,2010,27(4):424-427(in Chinese).周维友,胡炳成,刘祖亮.次卟啉二甲酯钴络合物均相选择性催化氧化环己烷[J].应用化学,2010,27(4):424-427. |
| [2] | Jain N,Kumar A.Metalloporphyrirt and Heteropoly Acid Catalyzed Oxidation of C＝NOH Bonds in an Ionic Liquid:Biomimetic Models of Nitric Oxide Synthase[J].Tetrahedron Lett,2005,46(15):2599-2602. |
| [3] | Groves J T,Viski P.Asymmetric Hydroxylation,Epoxidation,and Sulfoxidation Catalyzed by Vaulted Binaphthyl Metalloporphyrins[J].J Org Chem,1990,55 (11):3628-3634. |
| [4] | Feiters M C,Rowan A E,Nolte R J M.From Simple to Supramolecular Cytocbrome P450 Mimics[J].Chem Soc Rev,2000,29:375-384. |
| [5] | Boulatov R.Understanding the Reaction that Powers This World:Biomimetic Studies of Respiratory O2 Reduction by Cytochrome Oxidase[J].Pure Appl Chem,2004,76:303-319. |
| [6] | Meunier B,Bernadou J.Metal-Oxo Species in P450 Enzymes and Biomimetic Models.Oxo-Hydroxo Tautomerism with Water-Soluble Metalloporphyrins[J].Top Catal,2002,21:47-53. |
| [7] | Goh Y M,Nam W.Significant Electronic Effect of Porphyrin Ligand on the Reactivities of High-Valent Iron (Ⅳ) Oxo Porphyrin Cation Radical Complexes[J].Inorg Chem,1999,38 (5):914-920. |
| [8] | Jones R,Jayaraj K,Gold A,et al.Ground and Excited State Spectroscopic Probes of[(TMP) Fe (Ⅳ) O]+:The First Magnetic Circular Dichroism Study of a Model Peroxidase Compound I Intermediate[J].Inorg Chem,1998,37(12):2842-2843. |
| [9] | Brulé E,De Miguel Y R,Hii K K.Chemoselective Epoxidation of Dienes Using Polymer-supported Manganese Porphyrin Catalysts[J].Tetrahedron,2004,60(28):5913-5918. |
| [10] | Mohajer D,Tayebee R,Goudarziafshar H.Sodium Periodate Epoxidation of Alkenes Catalysed by Manganese Porphyrins[J].J Chem Res (S),1999:168-169. |
| [11] | Tangestaninejad S,Habib M H,Mirkhani V,et,al.Preparation of an Insoluble Polymer-supported Mn(Ⅲ) Porphyrin and Its Use as a New Alkene Epoxidation and Alkane Hydroxylation Catalyst[J].J Chem Res,2001,2001(10):444-445. |
| [12] | SHI Chunwei,CHEN Yepu.Application of Ozonation Reaction to Chemical Synthesis[J].Ghem lnd Eng Prog,2005,24 (9):985-988 (in Chinese).史春薇,陈烨璞.臭氧化反应应用研究进展[J].化工进展,2005,24(9):985-988. |
| [13] | WANG Jinjun,HAN Guangfan,WU Xuran,et al.Oxidation Reaction along Qy Axis and Rearrangement Reaction in E-Ring of Chlorophyll-a and Its Derivatives[J].Chinese J Org Chem,2005,25(1):101-108 (in Chinese).王进军,韩光范,邬旭然,等.叶绿素-a及其衍生物的Qy轴向氧化反应和E-环重排反应[J].有机化学,2005,25(1):101-108. |
| [14] | Chen G Q,Xu Z J,Zhou C Y,et al.Selective Oxidation of Terminal Aryl and Aliphatic Alkenes to Aldehydes Catalyzed byIron(Ⅲ) Porphyrins with Triflate as a Counter Anion[J].Chem Commun,2011,47:10963-10965. |
| [15] | SUN Chengguo,ZHOU Weiyou,HU Bingcheng,et al.A Facile Synthesis of 2,7,12,18-Tetramethyl-13,17-di (3-hydroxypropyl)porphyrin[J].Fine Chem,2009,26(9):920-922(in Chinese).孙呈郭,周维友,胡炳成,等.2,7,12,18-四甲基-13,17-二(3-羟基丙基)卟啉的改进合成[J].精细化工,2009,26(9):920-922. |
| [16] | Alder A D,Longo F R.On the Preparation of Metalloporphyrins[J].J lnorg Nucl Chem,1970,32:2443-2445. |
| [17] | Yang S J,Nam W.Water-soluble Iron Porphyrin Complex-catalyzed Epoxidation of Olefins with Hydrogen Peroxide and Tert-butyl Hydroperoxide in Aqueous Solution[J].lnorg Chem,1998,37:606-607. |
| [18] | Chen J,Che C M.A Practical and Mild Method for the Highly Selective Conversion of Terminal Alkenes into Aldehydes through Tpoxidation-isomerization with Ruthenium (Ⅳ)-porphyrin Catalysts[J].Angew Chem Irt Edit,2004,43:4950-4954. |
| [19] | YANG Weijun,GUO Cancheng,MAO Yanli,et al.Relationship between Electrochemical Behavior of Metalloporphyrins and Their Catalytic Performance for α-Pinene Oxidation[J].Chinese J Catal,2005,26 (5):360-364 (in Chinese).阳卫军,郭灿城,毛彦利,等.金属卟啉的电化学性质与其催化氧化α-蒎烯性能的关系[J].催化学报,2005,26(5):360-364. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分：
-
10%
-
20%
-
30%
-
40%
-
50%