An Efficient and Reusable Multifunctional Composite Magnetic Nanocatalyst for Knoevenagel Condensation

Nan Yao; Jin Tan; Yang Liu; Yu Lin Hu

doi:10.1055/s-0037-1612076

Synlett, Table of Contents

Synlett 2019; 30(06): 699-702
DOI: 10.1055/s-0037-1612076

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An Efficient and Reusable Multifunctional Composite Magnetic Nanocatalyst for Knoevenagel Condensation

Nan Yao

,

Jin Tan

,

Yang Liu

,

Yu Lin Hu *

College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang 443002, P. R. of China Email: huyulin@ctgu.edu.cn Email: huyulin1982@163.com

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Abstract

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Abstract

A range of multifunctional magnetic metal–organic framework nanomaterials consisting of various mass ratios of the metal–organic framework MIL-53(Fe) and magnetic SiO₂@NiFe₂O₄ nanoparticles were designed, prepared, characterized, and evaluated as heterogeneous catalysts for the Knoevenagel condensation. The as-fabricated nanomaterials, especially the nanocatalyst MIL-53(Fe)@SiO₂@NiFe₂O₄(1.0), showed good catalytic performance in the Knoevenagel condensation at room temperature as a result of synergistic interaction between the Lewis acid iron sites of MIL-53(Fe) and the active sites of the magnetic SiO₂@NiFe₂O₄ nanoparticles. In addition, the heterogeneous catalyst was readily recovered and a recycling test showed that it could be reused for five times without significant loss of its catalytic activity, making it economical and environmentally friendly.

Key words

metal-organic frameworks - magnetic nanocatalyst - Knoevenagel condensation - cooperative catalysis - heterogeneous catalysis - iron catalysis

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References

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38 2-Benzylidenemalononitrile; Typical ProcedureA mixture of PhCHO (5 mmol), malononitrile (5 mmol), EtOH (15 mL), and MIL-53(Fe)@SiO₂@NiFe₂O₄(1.0) (0.1 g) was magnetically stirred at r.t. until the reaction was complete (TLC). The catalyst that precipitated out from the mixture was collected by using an external magnet, washed with EtOH, and reused for consecutive cycles under the same reaction conditions. The product was crystallized from EtOH to give a white solid; yield: 755 mg (98%); mp 83.8–84.1 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.47–7.64 (m, 3 H, Ar-H), 7.78 (s, 1 H, CH), 7.85–7.94 (m, 2 H, Ar-H). MS: m/z [M + H]⁺ calcd for C₁₀H₇N₂: 155.1; found: 155.06; Anal. Calcd for C₁₀H₆N₂: C, 77.87; H, 3.90; N, 18.15. Found: C, 77.91; H, 3.92; N, 18.17.

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