RESUMO
Sustainable conversion of biomass, including fructose dehydration to 5-hydroxymethylfurfural (HMF), remains a challenge. Fructose can be selectively dehydrated to HMF in dimethyl sulfoxide (DMSO) without addition of an acid catalyst. The role of DMSO is examined starting with either fructose or HMF in DMSO/water. With increasing DMSO content, it is observed that fructose conversion, HMF selectivity, and post-reaction solution acidity increase. Although DMSO degradation to sulfuric acid is a potential source of acidity and reactivity, a barium chloride precipitation test demonstrates that sulfate ions are not detectable after reaction, suggesting that DMSO is stable during reaction at 120 °C and 150 °C with oxygen present. Instead, the majority of the acidic species produced are formic acid, levulinic acid, and humins. These acids have a minimal effect on fructose conversion in DMSO. These results suggest that DMSO promotes fructose conversion mainly through solvation effects and not as an origin of acid catalysis. For HMF stabilization, the optimal molar fraction of DMSO in water is 0.20-0.43. Overall, these results indicate that DMSO can promote fructose dehydration to HMF at 120 °C.