Application of an amino-functionalised metal–organic framework: an approach to a one-pot acid–base reaction

Abstract

The amino-functionalised metal–organic framework, MIL-101(Al)-NH₂, has been synthesized by using a solvothermal method and employed as a bifunctional acid–base catalyst for a one-pot, sequential deacetalization–Knoevenagel condensation reaction. In preliminary studies, the abilities of MIL-101(Al)-NH₂ to serve as an acid and base catalyst were explored separately by two typical acid- and base-catalysed reaction, that is, deacetalization of benzaldehyde dimethylacetal and Knoevenagel condensation of benzaldehyde with malononitrile. MIL-101(Al)-NH₂ was found to catalyse each of these reactions with high efficiency. MIL-101(Al)-NH₂ was then employed as a catalyst for the one-pot sequential deacetalization–Knoevenagel condensation reaction between benzaldehyde dimethylacetal and malononitrile. Benzylidenemalononitrile as the final product was successfully generated with a high yield via benzaldehyde over MIL-101(Al)-NH₂. In addition, the catalytic ability of MIL-101(Al)-NH₂ was demonstrated to be superior to those of conventional heterogeneous, homogeneous as well as other functionalised metal–organic framework catalysts. Finally, the results show that MIL-101(Al)-NH₂ can be reused as a catalyst for this process without significant loss of its activity.