Direct Catalytic Conversion of Furfural to Furan‐derived Amines in the Presence of Ru‐based Catalyst

Abstract

The production of amine intermediates from biomass is capturing increasing attention. Herein, a simple and efficient preparation of l furan‐derived amines was developed [e.g., 1‐(furan‐2‐yl)‐4‐methylpentan‐2‐amine] with high yield (up to 95 %) from (E)‐1‐(furan‐2‐yl)‐5‐methylhex‐1‐en‐3‐one. The catalyst used was Ru/C, and it was recyclable up to the fourth cycle. To further realize cost‐efficiency, a one‐reactor tandem concept was attempted. To this aim direct reaction from furfural was investigated. A high yield (74 %) towards 1‐(furan‐2‐yl)‐4‐methylpentan‐2‐amine could be achieved starting directly from furfural in the presence of methyl isobutyl ketone, NH3, H2, and Ru/C catalyst.

Highly selective and robust single-atom catalyst Ru1/NC for reductive amination of aldehydes/ketones

“…In contrast to the high efficiency of Ru 1 /NC-900 and Ru 1 /NC-900–800NH 3 SACs, the Ru 1 /NC-1000 catalyst with predominance of Ru NPs provides FAM yield of only 53% (Table 2 , entry 5), far inferior to the Ru single-atom catalysts. We also prepared other nanocatalysts including Ru/AC, Ru/Nb 2 O 5 , and Ru/HZSM-5 which were reported to be highly active for the reductive amination of furfural 19 , 45 , 46 . Under identical reaction conditions, the Ru/AC nanocatalyst gives an enhanced FAM yield (82%, Table 2 , entry 6) than Ru 1 /NC-1000, which can be due to the smaller and more exposed Ru particles on the AC support (Supplementary Fig.…”

Production of furans from C5 and C6 sugars in the presence of polar organic solvents

“…1,31,40,63,64 Biphasic operation has been applied to sugar dehydration at several aqueous-organic volume ratios, with mostly organic biphasic systems being reported to be the most beneficial in terms of sugar-to-furan selectivity. 1,20,40,[73][74][75] Under microwave heating, biphasic systems were shown to deliver higher yields when the organic solvent in use is a non-polar, microwave-silent solvent. 49 In such systems, the selective heating of the aqueous phase, while the organic phase stays relatively 'cold', has resulted in xylose-to-furfural selectivities up to 90 mol%.…”

“…1,[3][4][5][6][7]17,19 Furfural can be upgraded to THF, furan, butane and pentane diols, esters (e.g., furfuryl acetate, esters of levulinic acid and dimethyl pentanoate), and diesel alkanes. [1][2][3]6,7,17,[19][20][21][22] Furfural and HMF are generally produced by an acid-catalyzed dehydration of C5 and C6 sugars, respectively. [1][2][3]23 The most common substrates for the production of HMF are fructose and glucose.…”

Effect of Ni Metal Content on Emulsifying Properties of Ni/CNTox Catalysts for Catalytic Conversion of Furfural in Pickering Emulsions

“…[21,22] The relevance of FAL catalytic conversion comes from the large number of chemicals and biofuels that can be obtained from its transformation. [23][24][25][26][27] FAL can be converted to long-chain products by CÀ C coupling condensation reaction, [28,29] valuable fuel additives such as 2-methyltetrahydrofuran (2-MTHF) [30] and furfuryl ether (FFE), [31,32] and to value-added compounds such as furan by decarbonylation, [33] furfuryl alcohol by hydrogenation [34,35] and by hydrogenation/ ring rearrangement to cyclopentanone (CPO). [36][37][38][39][40] Particular focus has been put on the transformation of furfural to aliphatic cyclic molecules such as cyclopentanone and cyclopentanol because they are important intermediate in fine chemical industry with a broad range of application in the perfume, medicine, and agriculture field.…”

“…According to the US Department of Energy, furfural (FAL) has been selected as one of the top 30 building blocks obtained from biomass, [20] which can be converted directly or indirectly to more than 80 chemicals due to its high chemical reactivity [21,22] . The relevance of FAL catalytic conversion comes from the large number of chemicals and biofuels that can be obtained from its transformation [23–27] . FAL can be converted to long‐chain products by C−C coupling condensation reaction, [28,29] valuable fuel additives such as 2‐methyltetrahydrofuran (2‐MTHF) [30] and furfuryl ether (FFE), [31,32] and to value‐added compounds such as furan by decarbonylation, [33] furfuryl alcohol by hydrogenation [34,35] and by hydrogenation/ring rearrangement to cyclopentanone (CPO) [36–40] …”