One‐Step Reductive Amination of 5‐Hydroxymethylfurfural into 2,5‐Bis(aminomethyl)furan over Raney Ni

Abstract

Simultaneous reductive amination of C=O and C−OH in 5‐hydroxymethylfurfural (HMF) into C−NH2 in 2,5‐bis(aminomethyl)furan (BAMF) is challenging. In this work, reductive amination of C=O in HMF was firstly studied, in which HMF can be converted into 5‐hydroxymethyl furfurylamine (HMFA) with a 99.5 % yield over Raney Co catalyst. BAMF was then directly synthesized with 82.3 % yield from HMF over Raney Ni catalyst at 160 °C for 12 h. An even higher yield of 88.3 % could be obtained through a stepwise reductive amination process, in which the reaction started at 120 °C for the first 2 h over Raney Co mainly for amination of C=O and then continued at 160 °C for another 10 h over Raney Ni mainly for amination of C−OH. Under optimized reaction conditions, the catalyst could be reused four times without obvious loss in catalytic performance. XRD and XPS characterization of the reused catalyst indicated that the formation of Ni3N and the adsorption of alkyl amines could be the main reasons for the deactivation of the catalyst. Moreover, plausible reaction pathways were proposed to originate the detected by‐products according to the kinetic profiles.

Ambient‐Temperature Reductive Amination of 5‐Hydroxymethylfurfural Over Al2O3‐Supported Carbon‐Doped Nickel Catalyst

“…[15][16][17] The internal furyl-ring of HMF enables its great potential as a promising starting material in the synthesis of primary, secondary, and tertiary furyl-amines. [18][19][20] Nonetheless, the selective synthesis of amines from HMF remains scarce, encouraging the task-specific designation of reliable catalysts to create effective and green catalytic systems under mild conditions.…”

Reductive Amination, Hydrogenation and Hydrodeoxygenation of 5‐Hydroxymethylfurfural using Silica‐supported Cobalt‐ Nanoparticles

“…[20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] In order to valorize HMF, different reactions such as catalytic hydrogenations, hydrodeoxygenations, oxidations, and aminations have been applied. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] Applying these processes, a variety of compounds for example, 2,5-bis(hydroxymethyl)furan, 2,5-dimethylfuran, 2,5-dimethyltetrahydrofuran, hexanediols, levulinic acid, furan-2,5-dicarboxylic acid, alkanes, and bio-based amines could be accessed from HMF. [20]…”

“…[4,6,43] To prepare furan-based amines, catalytic reductive amination of HMF using molecular hydrogen constitute convenient methodology in which aldehyde group of HMF can be reacted with ammonia, primary and secondary amines to access different kinds of amines. [4][5][6][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] To perform reductive amination of HMF in more selective and efficient manner, the use of suitable catalyst systems is crucial. Regarding catalysts for this transformation, more frequently precious metal-based homogeneous, [44] and heterogeneous [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] systems based on, Rh, [45] Pt, [46] Pd, [47][48] Ru, [44,[49][50] and Au [51] were used.…”

“…[4][5][6][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] To perform reductive amination of HMF in more selective and efficient manner, the use of suitable catalyst systems is crucial. Regarding catalysts for this transformation, more frequently precious metal-based homogeneous, [44] and heterogeneous [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] systems based on, Rh, [45] Pt, [46] Pd, [47][48] Ru, [44,[49][50] and Au [51] were used. With respect to non-noble metal heterogeneous catalysts, Raney Ni, [52] Co, [53] Cu, [54][55] and Ni [56][57]…”

“…Regarding catalysts for this transformation, more frequently precious metal-based homogeneous, [44] and heterogeneous [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] systems based on, Rh, [45] Pt, [46] Pd, [47][48] Ru, [44,[49][50] and Au [51] were used. With respect to non-noble metal heterogeneous catalysts, Raney Ni, [52] Co, [53] Cu, [54][55] and Ni [56][57][58] based ones are known to catalyze the reductive amination of HMF. Despite these achievements the development of earth abundant metal-based catalysts, which should work in more efficient and selective manner under mild conditions, is still desired for reductive amination of HMF to produce biobased amines.…”