氯甲基化交联聚苯乙烯(CMCPS)微球的氯甲基与苯甲醛衍生物2-羟基-3.甲氧基苯甲醛(HMBA)发生傅克烷基化反应,形成改性微球HMBA-CPS；微球HMBA-CPS与环己二胺发生席夫碱反应,形成键合Salen配基的微球Salen-CPS；最后,使之与锰盐发生配位螯合反应,制得了固载有手性Mn(Ⅲ)-Salen配合物的固体催化剂Mn(Ⅲ)Salen-CPS,分别采用红外光谱、紫外/可见吸收光谱及扫描电子显微镜对固体催化剂的结构与形貌进行了表征和观察.研究了微球CMCPS与HMBA之间傅克烷基化反应的规律.结果表明,以AlCl3为Lewis酸催化剂,使用二氯甲烷与硝基苯混合溶剂,可有效地实施CMCPS与HMBA的傅克烷基化反应,制得固体催化剂Mn(Ⅲ)Salen-CPS.在V(CH2Cl2):V(NB)=10:1的混合溶剂中,40℃下反应10 h,可制得氯甲基转化率近于51％的改性微球HMBA-CPS.该制备途径具有简便、高效与快捷的特点.
参考文献
| [1] | Ballistreri F P,Brinchi L,Germani R,et al.Enantioselective Epoxidations of Alkenes Catalyzed by (Salen) Mn (Ⅲ) in Aqueous Surfactant Systems[J].Tetrahedron,2008,64:10239-10243. |
| [2] | Kuzniarska-Biernacka I,Pereira C,Carvalho A P,et al.Epoxidation of Olefins Catalyzed by Manganese(Ⅲ) Salen Complexes Grafted to Porous Heterostructured Clays[J].Appl Clay Sci,2011,53:195-203. |
| [3] | Kai Y,Gu Z C,Ji R N,et al.Heterogeneous Chiral Mn(Ⅲ) Salen Catalysts for the Epoxidation of Unfunctionalized Olefins Immobilized on Mesoporous Materials with Different Pore Sizes[J].Tetrahedron,2009,65:305-311. |
| [4] | Hu X Y,Fu X K,Xu J W,et al.A Novel Layered Organic Polymer-inorganic Hybrid Zinc Poly (styrenephenylvinylphosphonate)-phosphate Immobilized Chiral Salen Mn (Ⅲ) Catalyst Large-scale Asymmetric Epoxidation of Unfunctionalized Olefins[J].J Organomet Chem,2011,696:2797-2804. |
| [5] | Yang Y,Zhang Y,Hao S,et al.Tethering of Cu(Ⅱ),Co(Ⅱ) and Fe(Ⅲ) Tetrahydro-Salen and Salen Complexes onto Amino-functionalized SBA-15:Effects of Salen Ligand Hydrogenation on Catalytic Performances for Aerobic Epoxidation of Styrene[J].Chem Eng J,2011,171:1356-1366. |
| [6] | Tu X B,Fu X K,Hu X Y,et al.Chiral Salen Mn (Ⅲ) Immobilized on Sulfoalkyl Modified ZSP-IPPA as an Effective Catalyst for Asymmetric Epoxidation of Unfunctionalized Olefins[J].Inorg Chem Commun,2010,13:404-407. |
| [7] | Irene D,Vicente F,María J S.Chiral Manganese(Ⅲ) Salen Catalysts Immobilizedon MCM-41 and Delaminated Zeolites ITQ-2 and ITQ-6 through New Axial Coordinating Linkers[J].J Catal,2004,228(1):92-99. |
| [8] | Ren W S,Fu X K.Chiral Mn(Ⅲ) Salen Complexes Covalently Bonded on Zirconium Oligostyrenylphosphonate-phosphates as Catalysts for Enantioselective Epoxidation of Nonfunctionalized Alkenes[J].J Mol Catal A:Chem,2009,312:40-47. |
| [9] | Huang J,Fu X K,Wang C W,et al.Chiral Salen Mn (Ⅲ) Immobilized onto Sulfoalkyl-modified Zinc Poly (styrenephenylvinylphosphonate)-phosphate as Effective Catalysts for Epoxidation of Unfunctionalized Olefins[J].Micropor Mesopor Mater,2012,153:294-301. |
| [10] | Lou L L,Jiang S,Yu K,et al.Mesoporous Silicas Functionalized with Aminopropyl via co-Condensation:Effective Supports for Chiral Mn(Ⅲ) Salen Complex[J].Micropor Mesopor Mater,2011,142:214-220. |
| [11] | SHEN Yanling,GAO Baojiao,LI Gang.New Method of Preparing Chloromethylated Crosslinking Polystyrene Microspheres[J].Chem J Chinese Univ,2007,28 (3):580-583(in Chinese).申艳玲,高保娇,李刚.制备氯甲基化聚苯乙烯交联微球的新方法[J].高等学校化学学报,2007,28(3):580-583. |
| [12] | Bahramian B,Mirkhani V,Moghadam M,et al.Manganese (Ⅲ) Salen Immobilized on Montmorillonite as Biomimetic Alkene Epoxidation and Alkane Hydroxylation Catalyst with Sodium Periodate[J].Catal Commun,2006,7:289-296. |
| [13] | Lou L L,Yu K,Ding F,et al.Covalently Anchored Chiral Mn(Ⅲ) Salen-containing Ionic Species on Mesoporous Materials as Effective Catalysts for Asymmetric Epoxidation of Unfunctionalized Olefins[J].J Catal,2007,49:102-110. |
| [14] | Gong B W,Fu X K,Chen J X,et al.Synthesis of a New Type of Immobilized Chiral Salen Mn(Ⅲ) Complex as Effective Catalysts for Asymmetric Epoxidation of Unfunctionalized Olefins[J].J Catal,2009,262:9-17. |
| [15] | Huang J,Fu X K,Wang C W,et al.Chiral Salen Mn (Ⅲ) Immobilized onto Sulfoalkyl-modified Zinc Poly (styrenephenylvinylphosphonate)-phosphate as Effective Catalysts for Epoxidation of Unfunctionalized Olefins[J].Micropor Mesopor Mater,2012,153:294-301. |
| [16] | Maurya M R,Sikarwar S.Oxovanadium (Ⅳ) Complex of 2-(α-Hydroxyethyl)benzimidazole Covalently Bonded to Chloromethylated Polystyrene for Oxidation of Benzoin[J].Appl Catal A:Gen,2006,315:74-82. |
| [17] | Silva J A L da,Silva J J R F da,Pombeiro A J L.Oxovanadium Complexes in Catalytic Oxidations[J].Coord Chem Rev,2011,255:2232-2248. |
| [18] | WEI Rongqing,WANG Haiping,SHEN Bin,et al.Effect of Nitrobenzene on Preparation of Carboxyl Polystyrene by FriedelCrafts Acylation Reaction[J].J Chem Ind Eng,2005,56:1230-1235(in Chinese).魏荣卿,汪海萍,沈斌,等.硝基苯对傅克酰基化反应制备羧基化聚苯乙烯的影响[J].化工学报,2005,56:1230-1235. |
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%