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负载于斜发沸石上的 Pd(II)作为高效非均相催化剂用于通过 Ullmann 型偶联反应实现硫醇与芳基卤化物的 S-芳基化反应。

Pd (II) Immobilized on Clinoptilolite as a Highly Active Heterogeneous Catalyst for Ullmann Coupling-type S-arylation of Thiols with Aryl Halides.

机构信息

Department of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran.

Department of Biomaterials, College of Natural Resources, North Carolina State University, Raleigh, United States.

出版信息

Comb Chem High Throughput Screen. 2020;23(7):658-666. doi: 10.2174/1386207323666200415103239.

Abstract

BACKGROUND

There are a number of protocols for Ullmann coupling-type S-arylation reactions, many of them suffer from the use of homogenous and often corrosive catalyst, cumbersome workup procedures, and long reaction times. Besides, many of these reagents are expensive and non-recoverable, leading to the generation of a large amount of toxic waste particularly when large-scale applications are considered.

OBJECTIVE

The aim of this study was to prepare a new Pd catalyst bonded on the surface of zeolite as a heterogeneous catalyst.

METHODS

A heterogeneous palladium catalyst has been prepared by immobilizing Pd ions on Clinoptilolite. This novel developed heterogeneous catalyst was thoroughly examined for Ullmann coupling-type S-arylation reaction using different bases, solvents and 0.003 mg of the catalyst. The structural and morphological characterizations of the catalyst were carried out using XRD, TGA, BET and TEM techniques.

RESULTS

Highly efficient heterogeneous palladium catalyst has been developed by immobilizing Pd ions on Clinoptilolite, as one of the most abundant naturally occurring zeolites for Ullmann Sarylation. By using this method, we provide an efficient way to a wide variety of substituted thiolic compounds. Moreover, the catalyst is easily recovered using simple filtration and reused for 5 consecutive runs.

CONCLUSION

In this effort, we developed a new Pd catalyst bonded on the surface of zeolite as a substrate to prepare the heterogeneous catalyst. We demonstrate that this novel catalyst offers reliable and convincing data that may offer a valuable application in further developing the science and technology of Ullmann reaction protocols and allied industries. Additionally, the catalyst was reusable and kept its high activities over a number of cycles.

摘要

背景

乌尔曼型 S-芳基化反应有许多反应方案,其中许多方案都存在使用均相且通常腐蚀性催化剂、繁琐的后处理步骤和较长的反应时间等问题。此外,许多这些试剂价格昂贵且不可回收,导致在考虑大规模应用时会产生大量有毒废物。

目的

本研究旨在制备一种新型负载在沸石表面的钯催化剂作为多相催化剂。

方法

通过将钯离子固定在斜发沸石上,制备了一种多相钯催化剂。使用不同的碱、溶剂和 0.003mg 的催化剂,对这种新型开发的多相催化剂进行了乌尔曼型 S-芳基化反应的彻底研究。使用 XRD、TGA、BET 和 TEM 技术对催化剂的结构和形态特征进行了研究。

结果

通过将钯离子固定在斜发沸石上,开发出了一种高效的多相钯催化剂,斜发沸石是最丰富的天然沸石之一,可用于乌尔曼 S 芳基化反应。通过这种方法,我们为各种取代的硫醇化合物提供了一种有效的途径。此外,该催化剂可以通过简单的过滤回收,并在 5 次连续使用中重复使用。

结论

在这项工作中,我们开发了一种新型负载在沸石表面的 Pd 催化剂作为底物来制备多相催化剂。我们证明,这种新型催化剂提供了可靠和令人信服的数据,可能为进一步发展乌尔曼反应方案和相关行业的科学和技术提供有价值的应用。此外,该催化剂可重复使用,并在多次循环中保持高活性。

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