Microwave Assisted Synthesis of 5-Hydroxymethylfurfural from Starch in AlCl₃·6H₂O/DMSO/[BMIM]Cl System

Abstract

A successful protocol has been developed for the microwave assisted conversion of corn starch into 5hydroxymethylfurfural (HMF) utilizing aluminum chloride hexahydrate (AlCl 3 •6H 2 O) and 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid. HMF yield as high as 59.8 wt % was achieved at 150 °C within a short reaction time of 20 min. The dimethyl sulfoxide (DMSO)/[BMIM]Cl system was found to be tolerant to optimal water content which influenced the product distribution. Levulinic acid was detected in negligible quantities, and humin content could be controlled by varying different process parameters. Satisfactory results were achieved when waxy corn starch (HMF yield 64.9 wt %) and high amylose corn starch (HMF yield 51.1 wt %) were compared as potential feedstock alternatives to fructose and glucose. The work provided significant insight into the synthesis of HMF in a microwave environment from sustainably sourced biomass such as starch having high amylopectin content.

Recent Advances in the Microwave-Assisted Production of Hydroxymethylfurfural by Hydrolysis of Cellulose Derivatives—A Review

“…The capacity of AlCl 3 for the conversion of carbohydrates and polysaccharides into 5-HMF was studied. Rhagavan and co-workers employed a system involving aluminium chloride (AlCl 3 , 6 H 2 O) as a Lewis acid catalyst to perform the direct conversion of corn starch into 5-HMF [ 57 ]. This transformation was carried out in a commercial ionic liquid [BMIm]Cl.…”

Advances in polymer precursors and bio‐based polymers synthesized from 5‐hydroxymethylfurfural

“…94 The conversion of (24) to diisocyanates (25) was accomplished in two steps using diazides as the intermediates. 92 Derivatives from (23), such as diols (26) 98 and diamines (27) have also been prepared. 99 In addition to the derivatives aforementioned, continuous efforts are being put into upgrading HMF.…”

“…5‐hydroxymethylfurfural (HMF) is a promising platform chemical owing to its sustainability and functional groups available for further reactions. Due to the importance of HMF, research works have focused on several key aspects: (1) biological properties, such as the metabolism of HMF and toxicological effects; (2) synthesis of HMF including the catalysts used, the feedstocks used, and the solvent systems; (3) derivatives of HMF as biofuels precursors, fine chemicals, monomers for polymers; and (4) industrial production of HMF and its derivatives …”

“…1-9 5-hydroxymethylfurfural (HMF) is a promising platform chemical owing to its sustainability and functional groups available for further reactions. Due to the importance of HMF, research works have focused on several key aspects: (1) biological properties, such as the metabolism of HMF and toxicological effects; [10][11][12][13] (2) synthesis of HMF including the catalysts used, [14][15][16][17][18][19][20][21] the feedstocks used, 22,23 and the solvent systems; 19,[24][25][26][27] (3) derivatives of HMF as biofuels precursors, 28,29 fine chemicals, 30 monomers for polymers; 6,[30][31][32][33][34] and (4) industrial production of HMF and its derivatives. 23,32,35 One of the most important applications of HMF is to synthesize monomers for polymers, such as 2,5-furandicarboxylic acid (FDCA) and 2,5-bis(hydroxymethyl) furan (BHF).…”

The Direct Conversion of Cellulose into 5‐Hydroxymethylfurfural with CrCl3 Composite Catalyst in Ionic Liquid under Mild Conditions

“…It was found that imidazole ILs can effectively solubilize cellulose, and the highest solubility (25 wt.%) of cellulose was achieved in [C 4 mim]Cl under microwave irradiation. Furthermore, compared with traditional solvents, ILs have many advantages, including excellent thermostability, good solubility and negligible vapor pressure, which make them the most promising solvent for cellulose nowadays.…”