Preparation of 5‐(Aminomethyl)‐2‐furanmethanol by direct reductive amination of 5‐Hydroxymethylfurfural with aqueous ammonia over the Ni/SBA‐15 catalyst

Abstract

BACKGROUND 5‐(Aminomethyl)‐2‐furanmethanol (AMF), used widely in medicinal chemistry, is usually synthesized by the reductive amination of furfural or 5‐hydroxymethylfurfural (HMF) with ammonia. However, a challenging task when synthesizing this furyl primary amine is to enhance the selectivity of the product due to its high nucleophilicity. Conventional measures have used excessive liquid ammonia and precious metal catalysts. Usually, the molar ratio of ammonia to substrate is up to 30:1. This study employed aqueous ammonia to synthesize AMF by the direct reductive amination of HMF using the non‐noble metal Ni/SBA‐15 catalyst. RESULTS The Ni/SBA‐15 catalyst displayed higher catalytic selectivity in the reductive amination of HMF to AMF compared to other precious metal catalysts, such as Ru/C, Pd/C and Pt/C. The AMF yield of 89.8% was obtained at the relatively mild reaction temperature of 100 °C for 4 h. After the fifth cycle, an acceptable decrease in catalytic activity with 74.2% yield of AMF was observed. CONCLUSION An improved process was developed for preparing AMF by the reductive amination of HMF with aqueous ammonia using the non‐noble Ni/SBA‐15 catalyst. The high selectivity of nickel catalyst is attributed mainly to the moderate catalytic activity. Moreover, a small amount of water enhanced the yield of AMF by promoting the formation of ammonium ions to prevent the further side reaction of AMF with HMF. Results of recycling experiments and analyses showed that agglomeration, loss and oxidization of nickel species together with carbon deposition were responsible for the slight deactivation of the catalyst. © 2018 Society of Chemical Industry

Selective Catalysis for the Reductive Amination of Furfural Towards Furfurylamine by the Graphene-Co-Shelled Cobalt Nanoparticles

“…Analogous to furfural, reductive amination of HMF constitutes a significant fundamental route for the sustainable production of N-containing compounds from renewable biomass. Some of the reported literatures also suggested that the reactivity of HMF in the reductive amination with gaseous or aqueous ammonia was superior to furfural in terms of target yield and reaction conditions 21,22,40 , in according with our results in Entry 39 and 41. Other kinds of biomass-derived platforms such as phenolic model monomers (e.g., phenol and substituted phenol) derived from lignin were also tolerated in our experiments (Entry 46-61).…”

The Increasing Value of Biomass: Moving From C6 Carbohydrates to Multifunctionalized Building Blocks via 5‐(hydroxymethyl)furfural

“…Classical methods of reductive amination with borohydrides as reducing agents afford furanic amines 18 via formation of imine intermediates [48] . The same outcome can be achieved with more environmentally friendly transition metal‐catalyzed [27,45a,e,49] or biocatalyzed [50] methodologies.…”

“…5‐(Aminomethyl)‐2‐furanmethanol (AMF) containing both hydroxymethyl and aminomethyl groups at the furan ring is one of the most important aminated HMF‐derived building blocks with enormous synthetic potential. AMF can be prepared in good yields by reductive amination of HMF with ammonia in the presence of hydrogen by using either transition metal catalysts [45e,49a,b,f,51] or biocatalytic methods [45e,50,52] . Amination of AMF affords important monomer 2,5‐bis(aminomethyl)furan (BAMF) [49a] or other furanic amines including biologically active compounds [53] .…”

Using taurine to increase mesopores in Ce‐based metal–organic framework for enhancing the production of 5‐hydroxymethylfurfural and 5‐ethoxymethylfurfural from fructose

“…HMF has been identified as one of the most important biomassbased platform chemicals, because it can be transformed into many value-added chemicals. [1][2][3][4][5][6][7] HMF can be obtained from lignocellulose derivatives. 1,2 For the conversion of abundant and cheap fructose-based biomass into HMF or its derivatives, the activity of the catalyst and the reaction media can greatly influence fructose conversion and product selectivity.…”

“…HMF has been identified as one of the most important biomass‐based platform chemicals, because it can be transformed into many value‐added chemicals 1–7 . HMF can be obtained from lignocellulose derivatives 1,2 .…”