An Easy Scalable Approach to HMF Employing DMC as Reaction Media: Reaction Optimization and Comparative Environmental Assessment

In this work, bio-based platform molecule 5-hydroxymethylfurfural (HMF) was synthesised under mild conditions (90 °C) from D-fructose using as media a mixture of dimethyl carbonate:tetraethyl ammonium bromide (DMC:TEAB). This solvent system resulted in a efficient production of HMF in the presence of both Amberlyst-15 (heterogeneous catalyst) and BF3O(Et)2 (homogeneous catalyst). HMF was recovered from the reaction mixture with or without minimal work-up. It is noteworthy that this synthetic approach provided high yielding product also when performed in a large-scale. Quick reduction of HMF to the related 2,5-bis(hydroxymethyl)furan was also conducted to further confirm the proposed procedure. Besides, the materials efficiency metrics of the optimized DMC-based synthetic approach have been compared to alternative syntheses for HMF reported in the literature. This latter study takes into consideration synthetic routes that employ D-fructose as substrate, easy accessible catalysts and report detailed procedures and evidence of the isolation of HMF.In this work, bio-based platform molecule 5-hydroxymethylfurfural (HMF) was synthesised under mild conditions (90 degrees C) from D-fructose using as media a mixture of dimethyl carbonate:tetraethyl ammonium bromide (DMC:TEAB). This solvent system resulted in a efficient production of HMF in the presence of both Amberlyst-15 (heterogeneous catalyst) and BF3O(Et)(2) (homogeneous catalyst). HMF was recovered from the reaction mixture with or without minimal work-up. It is noteworthy that this synthetic approach provided high yielding product also when performed in a large-scale. Quick reduction of HMF to the related 2,5-bis(hydroxymethyl)furan was also conducted to further confirm the proposed procedure. Besides, the materials efficiency metrics of the optimized DMC-based synthetic approach have been compared to alternative syntheses for HMF reported in the literature. This latter study takes into consideration synthetic routes that employ D-fructose as substrate, easy accessible catalysts and report detailed procedures and evidence of the isolation of HMF