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在氯化胆碱:三乙醇胺这种可重复使用的低共熔溶剂中,实现高效的无碱和无配体钯催化酚类的芳基化反应。

Efficient base- and ligand-free palladium catalysed -arylation of phenols in choline chloride:triethanolamine as a reusable deep eutectic solvent.

作者信息

Abbasi Fatemeh, Sardarian Ali Reza

机构信息

Chemistry Department, College of Sciences, Shiraz University, Shiraz 71946-84795, Iran.

出版信息

R Soc Open Sci. 2024 Jun 5;11(6):240045. doi: 10.1098/rsos.240045. eCollection 2024 Jun.

Abstract

In this paper, we present a novel and sustainable approach using choline chloride:triethanolamine as a green, efficient and reusable deep eutectic solvent (DES) for Pd-catalysed -arylation reactions with Pd/BaSO (10%). By using the unique properties of DESs, we successfully achieved C-O bond formation without the need for additional solvents, bases and ligands. This solvent/catalyst system ([ChCl][TEA]) functioned as a dual catalyst and solvent system, enabling fast and environmentally friendly C-O bond formation from phenol derivatives and electron-deficient aryl halides, leading to remarkable yields under mild reaction conditions. To identify and characterize this DES, we employed differential scanning calorimetry, thermogravimetric analysis, Fourier-transform infrared spectroscopy, refractive index, viscosity, the potential of hydrogen (pH) and conductivity measurements. One of the remarkable advantages of this DES system is its exceptional stability. This solvent/catalyst system exhibited high stability throughout the reaction cycles, showing no significant loss of activity. As a result, this DES and catalyst (Pd/BaSO (10%)) can be easily recycled and re-used for up to three consecutive cycles, making it an economically and environmentally attractive option for organic reactions. Our approach offers several key benefits, including simple catalyst preparation, quick reaction times and excellent production efficiency.

摘要

在本文中,我们提出了一种新颖且可持续的方法,使用氯化胆碱:三乙醇胺作为绿色、高效且可重复使用的深共熔溶剂(DES),用于钯催化的苯酚衍生物与缺电子芳基卤化物的芳基化反应(钯负载量为10%的硫酸钡钯催化剂)。通过利用深共熔溶剂的独特性质,我们成功实现了碳 - 氧键的形成,无需额外的溶剂、碱和配体。这种溶剂/催化剂体系([ChCl][TEA])兼具双重功能,既作为催化剂又作为溶剂体系,能够在温和的反应条件下,使苯酚衍生物和缺电子芳基卤化物快速且环保地形成碳 - 氧键,从而获得显著的产率。为了鉴定和表征这种深共熔溶剂,我们采用了差示扫描量热法、热重分析、傅里叶变换红外光谱、折射率、粘度、氢离子电位(pH)和电导率测量。这种深共熔溶剂体系的显著优点之一是其卓越的稳定性。该溶剂/催化剂体系在整个反应循环中表现出高稳定性,活性没有明显损失。因此,这种深共熔溶剂和催化剂(10%的硫酸钡钯)可以轻松回收并重复使用多达三个连续循环,使其成为有机反应在经济和环境方面颇具吸引力的选择。我们的方法具有几个关键优势,包括催化剂制备简单、反应时间短和生产效率高。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3a9e/11295942/d2aa843525ce/rsos.240045.f007.jpg

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