疏水性全氟烷基磺酰亚胺固体酸催化酯化与Pechmann缩合
收稿日期: 2014-06-19
修回日期: 2014-07-13
网络出版日期: 2014-07-17
基金资助
国家自然科学基金(Nos.21172083, 21277055)资助项目.
Hydrophobic Perfluoroalkylsulfonyl Imide Solid Acid as Catalyst of Esterification and Pechmann Condensation
Received date: 2014-06-19
Revised date: 2014-07-13
Online published: 2014-07-17
Supported by
Project supported by the National Natural Science Foundation of China (Nos.21172083, 21277055).
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
马忠华 , 贺梦丽 , 张海娟 , 马敬中 , 原弘 . 疏水性全氟烷基磺酰亚胺固体酸催化酯化与Pechmann缩合[J]. 有机化学, 2014 , 34(11) : 2255 -2261 . DOI: 10.6023/cjoc201406027
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 runs with stable catalysis efficiency. On the other hand, H-PDVB-x-SSFAI was used to catalyze Pechmann condensation to give 7-hydroxyl coumarin under 140 ℃, affording ca. 90% of average isolated yield, and the catalyst could be cycled for 4 runs. Furthermore, the excellent catalytic performance is attributed to combination of excellent acidity and hydrophobicity.
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