From Lignocellulosic Biomass to Furans via 5‐Acetoxymethylfurfural as an Alternative to 5‐Hydroxymethylfurfural

Abstract

A facile pathway to furan derivatives from lignocellulosic biomass via 5-acetoxymethylfurfural (AMF) was developed. AMF possesses advantageous properties due to its less-hydrophilic acetoxymethyl group relative to the hydroxymethyl group of 5-hydroxymethylfurfural (HMF). The hydrophobicity and chemical stability of AMF allowed practical isolation and purification to afford a highly pure product of up to 99.9 %. AMF was produced in good to excellent yields under mild conditions from 5-chloromethylfurfural (CMF) and alkylammonium acetates, both of which could be obtained directly from lignocellulosic biomass. Heterogeneous reactions with polymer-supported alkylammonium acetates were also established; this showed the feasibility of a continuous process for this pathway. AMF could be transformed into various promising furanic compounds, such as 2,5-furandicarboxylic acid (FDCA), 2,5-furandimethanol (FDM), and 5-hydroxymethyl-2-furanoic acid (HFA), in high yields.

Total Synthesis of (−)‐Alstofolinine A through a Furan Oxidation/Rearrangement and Indole Nucleophilic Cyclization Cascade

“…[1] Furan derivatives have been broadly utilized in av ariety of fields,i ncluding polymer matrix composites and resins,a sw ell as more generally in organic synthesis. [1] Furan derivatives have been broadly utilized in av ariety of fields,i ncluding polymer matrix composites and resins,a sw ell as more generally in organic synthesis.…”

“…Furan-based compounds,w hich are predominately generated from biomass sources,a re af amily of important renewable green feedstocks. [1] Furan derivatives have been broadly utilized in av ariety of fields,i ncluding polymer matrix composites and resins,a sw ell as more generally in organic synthesis. [2] Furans can also be used to synthesize complex molecules via selective oxidation/bromination and rearrangement, [3] ap rocess known as Achmatowicz rearrangement.…”

Cellulose acetate as a convenient intermediate for the preparation of 5-acetoxymethylfurfural from biomass

“…17 Interestingly, reaction with alkylammonium acetates can be used to transform crude CMF into acetoxymethylfurfural (AMF). 18 The latter has also been proposed as a valuable HMF alternative, claiming that the acetyl moiety makes AMF hydrophobic, less reactive, and more versatile in terms of reactivity. 18 Interestingly, production of AMF by continuous reaction of fructose in supercritical acetic acid has been published.…”

“…18 The latter has also been proposed as a valuable HMF alternative, claiming that the acetyl moiety makes AMF hydrophobic, less reactive, and more versatile in terms of reactivity. 18 Interestingly, production of AMF by continuous reaction of fructose in supercritical acetic acid has been published. 19 However, we realized that the use of similar conditions for the direct conversion of cellulose derivatives into furanic compounds has not been reported, to the best of our knowledge.…”

An effective pathway for 5-brominemethylfurfural synthesis from biomass sugars in deep eutectic solvent

“…As shown in Fig. , it could be easily converted into other useful chemicals such as 2,5‐furandicarboxylic acid (FDCA), 2,5‐furandimethanol (FDM), and 5‐ethoxymethylfurfural (EMF) . However, the synthesis of 5‐BMF relied on high concentration of hydrobromic acid.…”