Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY® nickel

RANEY (R) Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH3 by simply adding or not adding 1.0 MPa H-2 into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H-2 in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H-2 leads to the formation of Ni3N and the deactivation of the catalyst.