疏水性全氟烷基磺酰亚胺固体酸催化酯化与Pechmann缩合有机化学.pdfVIP

DOI: 10.6023/cjoc201406027 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 疏水性全氟烷基磺酰亚胺固体酸催化酯化与Pechmann 缩合 马忠华 贺梦丽 张海娟 马敬中 原 弘* (华中农业大学理学院化学系 武汉 430070) 摘要 通过溶剂热的方法, 成功制备一类具有良好疏水性和强酸性的高分子, 聚二乙烯苯-对苯乙烯磺酰基全氟丁基 磺酰亚胺(记作 H-PDVB-0.3-SSFAI). 用于催化水相中长链脂肪酸的酯化反应, 可获得 88%转化率(24 h); 在直接酯化反 应体系中, 转化率最高能达到 95%～96% (5～6 h); 催化短链的乙酸和己酸的酯化反应, 伯醇和环己醇都能顺利进行, 其中, 环己醇转化率 87%～92% (4 h). 催化剂能循环使用至少 7 次. 在无溶剂条件下用于催化另一类酯化反应 Pechmann 缩合, 制备 7-羟基香豆素, 能在 140 ℃高温下循环使用4 次, 平均产率约 90%. H-PDVB-0.3-SSFAI 的良好疏 水性、强酸性和丰富多孔性, 是影响其催化效率的关键. 关键词 全氟烷基磺酰亚胺; 多相催化; 酯化; Pechmann 缩合 Hydrophobic Perfluoroalkylsulfonyl Imide Solid Acid as Catalyst of Esterification and Pechmann Condensation Ma, Zhonghua He, Mengli Zhang, Haijuan Ma, Jingzhong Yuan, Hong* (Department of Chemistry, College of Sciences, Huazhong Agricultural University, Wuhan 430070) Abstract Polydivinylbene-bound perfluoroalkylsulfonyl imide polymers with excellent acidity and hydrophobicity were prepared by copolymerization under solvothermal conditions (noted as H-PDVB-x-SSFAI). H-PDVB-x-SSFAI catalyzed the esterification of long chain fatty acid with methanol/ethanol in water, affording 88% conversion, which increased to 95% without additional water within 5～6 h. The catalytic esterification of short chain fatty acid with both primary alcohol and secondary alcohol was carried out smoothly, for example, 87%～92% of conversion was gave for cyclohexanol within 4 h. H-PDVB-x-SSFAI was cycled for at least seven