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水介质中过氧化氢对1-苯乙醇和甘油的铁催化氧化:氮配体对催化活性和选择性的影响

Iron-Catalyzed Oxidation of 1-Phenylethanol and Glycerol With Hydrogen Peroxide in Water Medium: Effect of the Nitrogen Ligand on Catalytic Activity and Selectivity.

作者信息

Ros Dimitri, Gianferrara Teresa, Crotti Corrado, Farnetti Erica

机构信息

Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Trieste, Italy.

Unità Operativa di Supporto di Trieste, Istituto Struttura della Materia, Consiglio Nazionale delle Ricerche, Trieste, Italy.

出版信息

Front Chem. 2020 Oct 9;8:810. doi: 10.3389/fchem.2020.00810. eCollection 2020.

DOI:10.3389/fchem.2020.00810
PMID:33195031
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7581906/
Abstract

The iron(II) complexes Fe(bpy) (bpy = 2,2'-bipyridine; OTf = CFSO) () and Fe(bpydeg) (bpydeg = , -bis(2-(2-methoxyethoxy)ethyl) [2,2'-bipyridine]-4,4'-dicarboxamide) (), the latter being a newly synthesized ligand, were employed as catalyst precursors for the oxidation of 1-phenylethanol with hydrogen peroxide in water, using either microwave or conventional heating. With the same oxidant and medium the oxidation of glycerol was also explored in the presence of and , as well as of two similar iron(II) complexes bearing tridentate ligands, ., Fe(terpy) (terpy = 2, 6-di(2-pyridyl)pyridine () and Fe(bpa) (bpa = bis(2-pyridinylmethyl)amine) (): in most reactions the major product formed was formic acid, although with careful tuning of the experimental conditions significant amounts of dihydroxyacetone were obtained. Addition of heterocyclic amino acids (, picolinic acid) increased the reaction yields of most catalytic reactions. The effect of such additives on the evolution of the catalyst precursors was studied by spectroscopic (NMR, UV-visible) and ESI-MS techniques.

摘要

铁(II)配合物Fe(bpy)(bpy = 2,2'-联吡啶;OTf = CFSO)()和Fe(bpydeg)(bpydeg = ,-双(2-(2-甲氧基乙氧基)乙基)[2,2'-联吡啶]-4,4'-二甲酰胺)(),后者是一种新合成的配体,被用作在水中用过氧化氢氧化1-苯乙醇的催化剂前体,使用微波或传统加热。在相同的氧化剂和介质中,还研究了在 和 以及两种带有三齿配体的类似铁(II)配合物存在下甘油的氧化反应,即Fe(terpy)(terpy = 2,6-二(2-吡啶基)吡啶()和Fe(bpa)(bpa = 双(2-吡啶基甲基)胺)():在大多数反应中,形成的主要产物是甲酸,尽管通过仔细调整实验条件可以获得大量的二羟基丙酮。添加杂环氨基酸(,吡啶甲酸)提高了大多数催化反应的产率。通过光谱(NMR、紫外可见)和ESI-MS技术研究了这些添加剂对催化剂前体演变的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/ab3bdd9911cf/fchem-08-00810-g0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/c4ff6937fcd2/fchem-08-00810-g0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/e013eaa284a8/fchem-08-00810-g0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/ed93e52ea2e0/fchem-08-00810-g0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/25e9d06387e0/fchem-08-00810-g0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/941accdd51aa/fchem-08-00810-g0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/0898e4328f22/fchem-08-00810-g0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/bf4715ea8313/fchem-08-00810-g0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/398fb266d46f/fchem-08-00810-g0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/ab3bdd9911cf/fchem-08-00810-g0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/c4ff6937fcd2/fchem-08-00810-g0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/e013eaa284a8/fchem-08-00810-g0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/ed93e52ea2e0/fchem-08-00810-g0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/25e9d06387e0/fchem-08-00810-g0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/941accdd51aa/fchem-08-00810-g0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/0898e4328f22/fchem-08-00810-g0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/bf4715ea8313/fchem-08-00810-g0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/398fb266d46f/fchem-08-00810-g0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/eaeb/7581906/ab3bdd9911cf/fchem-08-00810-g0009.jpg

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本文引用的文献

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Alcohol oxidation with HO catalyzed by a cheap and promptly available imine based iron complex.由一种廉价且易于获得的基于亚胺的铁配合物催化的HO对酒精的氧化反应。
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Chelating bis-N-heterocyclic carbene complexes of iron(ii) containing bipyridyl ligands as catalyst precursors for oxidation of alcohols.含有联吡啶配体的铁(II)螯合双-N-杂环卡宾配合物作为醇氧化反应的催化剂前体。
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