有机化学 ›› 2014, Vol. 34 ›› Issue (11): 2255-2261.DOI: 10.6023/cjoc201406027 上一篇    下一篇

研究论文

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   

  1. 华中农业大学理学院化学系 武汉 430070
  • 收稿日期:2014-06-19 修回日期:2014-07-13 出版日期:2014-11-25 发布日期:2014-07-17
  • 通讯作者: 原弘,yuanhong@mail.hzau.edu.cn E-mail:yuanhong@mail.hzau.edu.cn
  • 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

Ma Zhonghua, He Mengli, Zhang Haijuan, Ma Jingzhong, Yuan Hong   

  1. Department of Chemistry, College of Sciences, Huazhong Agricultural University, Wuhan 430070
  • Received:2014-06-19 Revised:2014-07-13 Online:2014-11-25 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

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.

Key words: perfluoroalkylsulfonyl imide, heterogeneous catalysis, esterification, Pechmann condensation