Efficient synthesis of bio‐based monomer 2,5‐bishydroxymethylfuran by the solvent‐free hydrogenation of 5‐hydroxymethylfurfural‐based deep eutectic mixture

Abstract

BACKGROUND: Biomass holds the promise to provide a sustainable future for the chemical industry. 2, 5-Bishydroxymethylfuran (BHMF) is a versatile bio-based diol with a broad range of potential applications in many polymeric materials, artificial fibers and drugs. However, the controlling of the BHMF selectivity in hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) with complex transformation pathways is always a great challenge especially under solvent-free conditions in which many side reactions may occur due to its rich reducible groups.RESULTS: A facile and effective approach was developed for the selective synthesis of BHMF by solvent-free hydrogenation of a deep eutectic mixture consisting of HMF (75 wt%) and choline chloride (ChCl), by which a BHMF selectivity up to 94.6% was gained at full HMF conversion over Raney Co at 100°C in 4 h. In addition, the HMF conversion and selectivity toward BHMF can be regulated and controlled through altering the strength of hydrogen-bonding interactions of HMF-based deep eutectic mixtures (ChCl-HMF mixtures). CONCLUSION:We developed an effective approach that allows the solvent-free synthesis of BHMF via hydrogenation of HMFbased deep eutectic mixtures. The extraordinary BHMF selectivity in the solvent-free hydrogenation of HMF is reasonably attributed to the hydrogen-bonding interactions formed between ChCl and HMF/BHMF which greatly suppresses the side reactions of HMF and the over-reduction of BHMF. Scheme 1. Hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bishydroxymethylfuran (BHMF) and probable over-reduction products. MFA, 5-methylfurfuryl alcohol; BHMTHF, 2,5-bis-(hydroxymethyl)tetrahydrofuran; DMF, 2,5-dimethylfuran.Synthesis of bio-based monomer 2,5-bishydroxymethylfuran www.soci.org

Solvent‐Free Hydrogenation of 5‐Hydroxymethylfurfural and Furfural to Furanyl Alcohols and their Self‐Condensation Polymers

“…Thus, it is highly desirable to develop an effective solvent‐free system for the hydrogenation of HMF/FF, but few works focus on this field. Cobalt species was confirmed to be efficient for the conversion of highly concentrated HMF (75 wt%) to selectively synthesize BHMF in our previous work [5] . On this basis, cobaltic nitrogen‐doped carbon (Co−NC) catalysts with more ordered and stable structure were prepared from ZIF‐67 through calcination at various temperatures and tested for the solvent‐free hydrogenation of HMF/FF to BHMF/FFA in this work.…”

“…Cobalt species was confirmed to be efficient for the conversion of highly concentrated HMF (75 wt%) to selectively synthesize BHMF in our previous work. [5] On this basis, cobaltic nitrogen-doped carbon (CoÀ NC) catalysts with more ordered and stable structure were prepared from ZIF-67 through calcination at various temperatures and tested for the solvent-free hydrogenation of HMF/FF to BHMF/FFA in this work. As expected, CoÀ NC calcinated at 600 °C (CoÀ NC-600) exhibits a desired catalytic activity for the solvent-free hydrogenation reaction, which provided a full conversion of HMF/FF with a BHMF/FFA yield higher than 90 % at the optimal conditions.…”

Deep Eutectic Solvents and Multicomponent Reactions: Two Convergent Items to Green Chemistry Strategies

“…Selectivity of such conversion goes up to 94.6 % over Raney Co at 100 °C. BHMF can be transformed into bishydroxymetyltetrahydofuran (BHMFHF) in a subsequent reduction in the reaction conditions [128] (Scheme 9 ).…”

Improved Bio-Synthesis of 2,5-bis(hydroxymethyl)furan by Burkholderia contaminans NJPI-15 With Co-substrate

“…BHMF is the hydrogenation product of the formyl group in HMF and is a versatile building block for the synthesis of polymers, drugs, and macrocycle polyether compounds. Additionally, it is known that fatty acid diesters of BHMF have applications as biodiesel additives and nonionic surfactants ( Petri et al, 2018 ; Xu et al, 2018 ; Wang et al, 2020 ).…”