催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (9): 1690-1696.DOI: 10.1016/S1872-2067(12)60654-8

• 研究论文 • 上一篇    下一篇

Ionic-liquid-catalyzed green synthesis of coumarin derivatives under solvent-free conditions

Hamid Reza Shaterian, Morteza Aghakhanizadeh   

  1. Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran
  • 收稿日期:2012-08-10 修回日期:2012-10-23 出版日期:2013-09-16 发布日期:2013-08-28
  • 通讯作者: Hamid Reza Shaterian

Ionic-liquid-catalyzed green synthesis of coumarin derivatives under solvent-free conditions

Hamid Reza Shaterian, Morteza Aghakhanizadeh   

  1. Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran
  • Received:2012-08-10 Revised:2012-10-23 Online:2013-09-16 Published:2013-08-28

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摘要：

Brönsted acidic ionic liquids, namely 2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium dihydrogen phosphate, (4-sulfobutyl)tris(4-sulfophenyl)phosphonium hydrogen sulfate, and triphenyl(propyl-3-sulfonyl)phosphonium toluenesulfonate, catalyzed efficient Pechmann condensation of phloroglucinol with β-keto ethyl/ methyl esters. 5,7-Dihydroxy-4-methylcoumarin and 5,7-dihydroxy-4-phenylcoumarin were prepared in good to excellent yields under mild, ambient, and solvent-free conditions. Pyrano[2,3-h] coumarins were then prepared by one-pot three-component reactions of 5,7-dihydroxy-4-subsituted coumarin, malononitrile, and aldehydes in the presence of catalytic amounts of Brönsted basic ionic liquids, namely 2-hydroxyethylammonium formate, 3-hydroxypropanaminium acetate, 1-butyl-3-methylimidazolium hydroxide, pyrrolidinium formate, and pyrrolidinium acetate, under thermal solvent-free conditions. The catalysts are environmentally benign and can be easily prepared, stored, and recovered without significant loss of activity.

关键词: Ionic liquid, Pechmann reaction, Solvent-free synthesis, Phloroglucinol, Pyrano[2,3-h]coumarin

Abstract:

Brönsted acidic ionic liquids, namely 2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium hydrogen sulfate, N-methyl-2-pyrrolidonium dihydrogen phosphate, (4-sulfobutyl)tris(4-sulfophenyl)phosphonium hydrogen sulfate, and triphenyl(propyl-3-sulfonyl)phosphonium toluenesulfonate, catalyzed efficient Pechmann condensation of phloroglucinol with β-keto ethyl/ methyl esters. 5,7-Dihydroxy-4-methylcoumarin and 5,7-dihydroxy-4-phenylcoumarin were prepared in good to excellent yields under mild, ambient, and solvent-free conditions. Pyrano[2,3-h] coumarins were then prepared by one-pot three-component reactions of 5,7-dihydroxy-4-subsituted coumarin, malononitrile, and aldehydes in the presence of catalytic amounts of Brönsted basic ionic liquids, namely 2-hydroxyethylammonium formate, 3-hydroxypropanaminium acetate, 1-butyl-3-methylimidazolium hydroxide, pyrrolidinium formate, and pyrrolidinium acetate, under thermal solvent-free conditions. The catalysts are environmentally benign and can be easily prepared, stored, and recovered without significant loss of activity.

Key words: Ionic liquid, Pechmann reaction, Solvent-free synthesis, Phloroglucinol, Pyrano[2,3-h]coumarin