Highly Efficient Production of 5-Methoxymethylfurfural from Fructose in Dimethyl Sulfoxide/Amberlyst-15 Catalytic System

Abstract

With the dwindling availability of fossil fuel resources and the dramatic increase in demand, 5-methoxymethylfurfural (MMF) obtained from renewable biomass resources has great potential as a fossil fuel alternative. In this work, a high yield (80.5%) of MMF was obtained from fructose catalyzed by Amberlyst-15 with the assistance of dimethyl sulfoxide (DMSO) in methanol at 100 °C for 10 h. Based on a detailed investigation of the reaction mechanism through the effects of DMSO, Amberlyst-15, reaction time, and reaction temperature on MMF yield and the existence of intermediates proved by FTIR, a two-step pathway was proposed:(1) DMSO and H ion on Amberlyst-15 act as a joint-catalyst [DMSOH] + , facilitating the dehydration of fructose into 5hydroxymethylfurfural (HMF), and (2) [DMSOH] + assists the etherification of HMF with methanol into MMF, which is the ratedetermining step. This finding expands the concept of biomass conversion into biomass fuels and plays a vital role in catalyst screen and design, reaction medium selection, and industrial applications.

Highly Efficient 5-Hydroxymethylfurfural Production from Glucose over Bifunctional SnOx/C catalyst

“…Therefore, their replacement by heterogeneous catalysts especially solid acids is highly recommended. Significant advancements in heterogeneous solid acid catalysts, such as zeolites, ,, ion exchange resins and metal oxides, ,, have been achieved; however, higher HMF yield could not be realized in batch reactions. Some ion exchange resins and metal oxides showed poor cycling performance in water or other highly polar media because of their low hydrothermally stability, , therefore, the development of catalysts with good stability and high acid capacity is considered crucial for promoting efficient conversion of glucose …”

Insight into the dehydration of high-concentration fructose to 5-hydroxymethylfurfural in oxygen-containing polar aprotic solvents

“…Fructose is soluble in low carbon alcohols (such as methanol, ethanol, and isopropanol), for example, the solubility for fructose in methanol is 85 g L −1 , 17 but alcohols are prone to etherification and acetalization reactions with 5-HMF, as shown by Yang et al , 24 who achieved 80.5% yield of 5-methoxymethylfurfural using a mixed solvent system of DMSO and methanol. The 5-HMF generated by the dehydration reaction continues to react with the alcohol, which protects the stability of the furan ring and inhibits its further ring-opening degradation.…”

Continuous‐Flow Synthesis of 5‐Hydroxymethylfurfural, Furfural from Monosaccharides: A Simple, Fast, and Practical Method

“…Thus, the synthesis of HMF from carbohydrates has attracted considerable attention as a crucial step in the manufacturing of biofuels. [1,[15][16][17] Several attempts have been extensively investigated for the preparation of HMF from fructose using Brønsted or Lewis acidic catalysts such as mineral acids, [18] amberlyst-15, [19] phosphate-functionalized porous organic polymers, [20] p-sulfonic acid calix [4]arene, [21] metalorganic frameworks, [6] acidic zeolite, [22][23] metal chlorides, [24] and carbon-based solid acid. [25] Ionic liquids have been known as green reaction media for the dissolution of carbohydrates and conversion of biomass into valuable compounds.…”