催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (1): 162-165.DOI: 10.3724/SP.J.1088.2011.00531

• 研究论文 • 上一篇    下一篇

酰胺类酸性离子液体催化 Oxa-Michael 加成反应

郭辉, 王君良, 李霞, 吕德水, 林贤福   

  1. 浙江大学化学系, 浙江杭州 310027
  • 收稿日期:2010-06-05 修回日期:2010-10-18 出版日期:2011-01-13 发布日期:2014-05-22

Oxa-Michael Addition Catalyzed by Amide-Based Acidic Ionic Liquids

GUO Hui, WANG Junliang, LI Xia, LÜ Deshui, LIN Xianfu*   

  1. Department of Chemistry, Zhejiang University, Hangzhou 310027, Zhejiang, China
  • Received:2010-06-05 Revised:2010-10-18 Online:2011-01-13 Published:2014-05-22

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1208

被引次数

53

摘要： 设计合成并表征了 N-甲基吡咯烷酮磷酸盐 ([NMPH]H2PO4)、己内酰胺磷酸盐 ([NHCH]H2PO4)、N,N′-二甲基甲酰胺磷酸盐 ([DMFH]H2PO4) 和 N,N′-二甲基乙酰胺磷酸盐 ([DMEH]H2PO4) 等酰胺类质子酸离子液体; 将其用于 β-苯乙醇和丁烯酮的 Oxa-Michael 加成反应中, 考察了离子液体阳离子结构、离子液体用量、底物配比、反应温度和时间对 Oxa-Michael 加成反应性能的影响. 结果表明, 以 [NMPH]H2PO4 为催化剂, β-苯乙醇/丁烯酮 = 1/2 (摩尔比), 室温反应 24 h 时, 苯乙醇的转化率可达 95%. 离子液体重复使用 5 次后, 依然保持较高的催化活性. 通过比较发现, 酰胺类酸性离子液体催化活性高于具有相同阴离子的咪唑离子液体, 表明阳离子结构对加成反应性能的影响很大. 据此提出了酰胺类离子液体催化 Oxa-Michael 加成可能的反应机理, 并通过核磁和对比实验进行了证明.

关键词: 酰胺类酸性离子液体, 催化, Oxa-Michael 加成, &beta, -苯乙醇, 丁烯酮

Abstract: A series of acidic ionic liquids, including N-methyl-2-pyrrolidonium dihydrogen phosphate ([NMPH]H2PO4), caprolactam dihydrogen phosphate ([NHCH]H2PO4), N,N′-dimethylformamide dihydrogen phosphate ([DMFH]H2PO4), and N,N′-dimethylacetamide dihydrogen phosphate ([DMEH]H2PO4), were synthesized and characterized. Oxa-Michael addition of β-phenylethanol to methyl vinyl ketone (MVK) was used as a model reaction. The effects of cation structure, ionic liquid amount, β-phenylethanol/MVK ratio, reaction temperature, and reaction time were measured. Under the optimized conditions of n(β-phenylethanol):n(MVK) = 1:2, 25 °C, 24 h and using [NMPH]H2PO4 as catalyst, the β-phenylethanol conversion was 95%. The ionic liquid was stable and could be reused at least 5 times with a slight loss of activity. All the amide-based acidic ionic liquids gave higher conversion compared with imidazolium acidic ionic liquid, which showed that the effect of cation structure was important. A possible reaction mechanism was proposed and the evidence for the role of amide-based acidic ionic liquids in Oxa-Michael addition was given.

Key words: amide-based acidic ionic liquid, catalysis, Oxa-Michael addition, β-phenylethanol, methyl vinyl ketone