Metal-Organic Framework MIL-101-NH2-Supported Acetate-Based Butylimidazolium Ionic Liquid as a Highly Efficient Heterogeneous Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones
Metal-Organic Framework MIL-101-NH2-Supported Acetate-Based Butylimidazolium Ionic Liquid as a Highly Efficient Heterogeneous Catalyst for the Synthesis of 3-Aryl-2-oxazolidinones
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DOI：
10.1021/acs.langmuir.8b03153
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发表时间：
2019-01-15
期刊：
影响因子：
3.9
通讯作者：
Ji, M.
中科院分区：
文献类型：
--
作者：
Chong, S. Y.;Wang, T. T.;Ji, M.
以MIL-101-NH2为载体，采用“瓶装法”制备了一种新型的多相催化剂--1-丁基-3-甲基咪唑乙酸酯离子液体(IL(OAc-)-MIL-101-NH2)。在MIL-101-NH_2纳米笼中，MIL-101-NH_2‘-S胺基与1，1’-甲酰基二咪唑缩合产物与1-溴丁烷反应，中间产物用醋酸钾交换，初步制备了BmiOAc的离子液体。用粉末X射线衍射仪、扫描电子显微镜、傅立叶变换红外光谱、DRS-UV-Vis、氮气吸附-脱附和元素分析等手段对IL(OAc-)-MIL-101-NH2的结构和物化性能进行了表征。结果表明，BmiOAc通过酰胺基固定在MIL-101-NH2骨架上，并以单分子形式固定在纳米笼中。IL(OAc-)-MIL-101-NH2复合材料具有良好的催化活性，催化合成了3-芳基-2-恶唑酮，产率可达92%。它可以重复使用六次而不会有明显的活性损失，并对底物表现出明显的尺寸选择性。推测金属-有机骨架载体的孔径大小可以控制反应物的扩散动力学。
A novel heterogeneous catalyst, the ionic liquid (IL) of 1-butyl-3-methylimidazolium acetate (BmimOAc) immobilized on MIL-101-NH2, denoted as IL(OAc-)-MIL-101-NH2, was prepared by the "ship-in-a-bottle" strategy. The IL of BmimOAc was prepared in the MIL-101-NH2 nanocages primordially, in which the condensation product of MIL-101-NH2's amine group with 1,1'-carbonyldiimidazole (CDI) reacted with 1-bromo butane, and then the intermediate exchanged with potassium acetate. The structure and physicochemical properties of IL(OAc-)-MIL-101-NH2 were characterized by powder X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, DRS UV-vis, nitrogen adsorption-desorption, and elemental analysis. The results indicated that BmimOAc was anchored in the MIL-101-NH2 skeleton via the acylamino group and confined in the nanocages in the form of a single molecule. The composite material of IL(OAc-)-MIL-101-NH2 exhibited excellent catalytic activity and catalytically synthesized 3-aryl-2-oxazolone in an excellent yield of 92%. It can be reused up to six times without noteworthy loss of its activity and demonstrated distinct size-selective property for substrates. It was conjectured that the diffusion kinetics of reactants could be controlled by the aperture size of the metal-organic framework support.