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负载于二甲双胍-石墨相氮化碳纳米片上的铜(II)作为高效催化剂对苄醇进行串联氧化酰胺化反应。

Tandem oxidative amidation of benzylic alcohols by copper(II) supported on metformin-graphitic carbon nitride nanosheets as an efficient catalyst.

作者信息

Ghafuri Hossein, Ghafori Gorab Mostafa, Dogari Haniyeh

机构信息

Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, 16846-13114, Tehran, Iran.

出版信息

Sci Rep. 2022 Mar 10;12(1):4221. doi: 10.1038/s41598-022-07543-3.

DOI:10.1038/s41598-022-07543-3
PMID:35273221
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8908756/
Abstract

In this research, an efficient heterogeneous catalyst based on graphitic carbon nitride nanosheets (CN) has been reported. The CN was functionalized by 1,3-dibromopropane as a linker (CN-Pr-Br) and subsequently modified with metformin (CN-Pr-Met). Furthermore, the copper(II) was coordinated on modified CN (CN-Pr-Met-Cu(II)) and during this process, 7.94% copper(II) was loaded into the catalyst structure. The synthesized catalyst was evaluated by various techniques including fourier-transform infrared spectroscopy (FT-IR), energy dispersive X-ray spectroscopy (EDS), field emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and inductively coupled plasma atomic emission spectroscopy (ICP-OES). CN-Pr-Met-Cu(II) was used as a catalyst in the synthesis of amides via the oxidation of benzyl alcohols. The conditions of this reaction were optimized in terms of temperature, time, amount of catalyst, type of base, oxidant, and solvent. Moreover, a variety of amides with an efficiency of 75-95% were synthesized. The reaction was carried out in the presence of benzyl alcohols, amine hydrochloride salts, tert-butyl hydroperoxide (TBHP), CaCO, and CN-Pr-Met-Cu(II) at 80 °C of acetonitrile solvent. The synthesized catalyst can be easily separated from the reaction medium and reused for 7 consecutive runs without a significant reduction in reaction efficiency.

摘要

在本研究中,报道了一种基于石墨相氮化碳纳米片(CN)的高效非均相催化剂。通过1,3 - 二溴丙烷作为连接剂对CN进行功能化(CN - Pr - Br),随后用二甲双胍进行修饰(CN - Pr - Met)。此外,将铜(II)配位在修饰后的CN上(CN - Pr - Met - Cu(II)),在此过程中,7.94%的铜(II)负载到催化剂结构中。通过傅里叶变换红外光谱(FT - IR)、能量色散X射线光谱(EDS)、场发射扫描电子显微镜(FE - SEM)、热重分析(TGA)、X射线衍射(XRD)和电感耦合等离子体原子发射光谱(ICP - OES)等多种技术对合成的催化剂进行了评估。CN - Pr - Met - Cu(II)被用作通过苄醇氧化合成酰胺的催化剂。该反应的条件在温度、时间、催化剂用量、碱的类型、氧化剂和溶剂方面进行了优化。此外,还合成了多种效率为75 - 95%的酰胺。反应在苄醇、胺盐酸盐、叔丁基过氧化氢(TBHP)、CaCO和CN - Pr - Met - Cu(II)存在下,于80°C的乙腈溶剂中进行。合成的催化剂可以很容易地从反应介质中分离出来,并连续重复使用7次,而反应效率没有显著降低。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/98a31a95f1e9/41598_2022_7543_Fig8_HTML.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/a4fbb4f06733/41598_2022_7543_Fig1_HTML.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/0aa840a52072/41598_2022_7543_Fig4_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/176c9cf55946/41598_2022_7543_Fig5_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/e4b79ff15afe/41598_2022_7543_Fig6_HTML.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/280e/8913806/f9a54726376c/41598_2022_7543_Fig7_HTML.jpg
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