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以碳酸丙烯酯为溶剂,用低负载量氯化铁催化活化芳烃的环保高效傅克酰基化反应:范围及机理探究

Eco-friendly and efficient Friedel-Crafts acylation of activated arenes catalyzed with low-loaded ferric chloride in propylene carbonate as the solvent: scope and mechanistic insights.

作者信息

Cherif Saif Eddine, Chehaibi Mayssa, Raddadi Rafif, Fustier-Boutignon Marie, Lakhdar Sami, Kraïem Jamil

机构信息

Laboratoire de Développement Chimique, Galénique et Pharmacologique des Médicaments, Faculté de Pharmacie de Monastir, Université de Monastir Rue Avicenne 5000 Monastir Tunisia

CNRS, Université Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR5069) 118 Route de Narbonne, 31062 Cedex 09 Toulouse France

出版信息

RSC Adv. 2025 Sep 1;15(38):31088-31094. doi: 10.1039/d5ra03638k. eCollection 2025 Aug 29.

Abstract

The Friedel-Crafts acylation of arenes is a fundamental reaction extensively employed in both academic research and industrial applications. A significant limitation of this reaction is the requirement for stoichiometric amounts of Lewis acid catalysts, which are typically sensitive and generate considerable waste. In this study, we present an improved catalytic approach for the Friedel-Crafts acylation of activated arenes. Using acyl chlorides and acid anhydrides as acylating agents, the reaction is efficiently catalyzed by 5 mol% iron(iii) chloride in propylene carbonate, an environmentally friendly solvent that outperforms traditional solvents in maintaining high reaction efficiency under catalytic conditions. This green methodology demonstrates high effectiveness and broad applicability, yielding aromatic ketones in good to excellent yields. Preliminary DFT calculations were carried out to rationalize the mechanism of the reaction.

摘要

芳烃的傅克酰基化反应是一种在学术研究和工业应用中都广泛使用的基础反应。该反应的一个显著局限性是需要化学计量的路易斯酸催化剂,这些催化剂通常很敏感且会产生大量废物。在本研究中,我们提出了一种用于活化芳烃傅克酰基化反应的改进催化方法。使用酰氯和酸酐作为酰化剂,该反应在碳酸丙烯酯中由5 mol%的三氯化铁高效催化,碳酸丙烯酯是一种环境友好型溶剂,在催化条件下保持高反应效率方面优于传统溶剂。这种绿色方法显示出高效性和广泛的适用性,能以良好至优异的产率生成芳香酮。进行了初步的密度泛函理论计算以阐明该反应的机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4d77/12400303/df85f3c2db24/d5ra03638k-s1.jpg

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