Reductive Amination of 5-Hydroxymethylfurfural to 2,5-Bis(aminomethyl)furan over Alumina-Supported Ni-Based Catalytic Systems.

Mono- and bimetallic Ni-based catalysts were prepared by screening 6 supports and 14 secondary metals for reductive amination of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(aminomethyl)furan (BAMF), among which γ-Al O and Mn were the best candidates. By further optimization of the reaction conditions at 0.4 g catalyst loading for 0.5 g substrate of 5-HMF and 160 °C of reaction temperature, 10Ni/γ-Al O and 10NiMn(4 : 1)/γ-Al O achieved the highest BAMF yields of 86.3 and 82.1 %, respectively. Although the BAMF yield values were comparable with that over Raney Ni, the turnover frequencies based on the initial BAMF yield and unit weight of Ni for 10NiMn(4 : 1)/γ-Al O , 10Ni/γ-Al O , and Raney Ni were calculated as 0.41, 0.09, and 0.04 h , respectively. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy showed that the existence of MnO well dispersed on the γ-Al O support and its electron transfer effect with Ni particles on the surface of the support contributed to the high efficiency and better recyclability for the five-time reused 10NiMn(4 : 1)/γ-Al O catalyst.