Going Beyond the Limits of the Biorenewable Platform: Sodium Dithionite-Promoted Stabilization of 5-Hydroxymethylfurfural

Rafael F A Gomes; Yavor N Mitrev; Svilen P Simeonov; Carlos A M Afonso

doi:10.1002/cssc.201800297

Going Beyond the Limits of the Biorenewable Platform: Sodium Dithionite-Promoted Stabilization of 5-Hydroxymethylfurfural

ChemSusChem. 2018 May 25;11(10):1612-1616. doi: 10.1002/cssc.201800297. Epub 2018 Apr 18.

Authors

Rafael F A Gomes¹, Yavor N Mitrev², Svilen P Simeonov^{1

2}, Carlos A M Afonso¹

Affiliations

¹ Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003, Lisboa, Portugal.
² Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 9, 1113, Sofia, Bulgaria.

PMID: 29608817
DOI: 10.1002/cssc.201800297

Abstract

The lack of thermal and storage stability and occurrence of side reactions during the processing of 5-hydroxymethylfurfural (5-HMF) limits its potential as biorenewable platform molecule. The addition of small amounts of the readily available sodium dithionite has a remarkable effect on promoting the stability of 5-HMF and inhibiting side reactions, thus helping to circumvent such limitations. The addition of sodium dithionite led to improvements in thermal stability (120 °C, 4 h, neat; 100 % vs. 37 %), under distillation (yield: 85 % vs. 52 %), and in a wide range of reactions, including 5-HMF synthesis under biphasic conditions (yield: 98 % vs. 67 %; purity: 92 % vs. 83 %) and 5-HMF transformations, such as Knoevenagel condensation with Meldrum's acid (yield: 96 % vs. 74 %), Cannizaro reaction (yield: quantitative vs. 83 %), and condensation with primary diamines to give pyridinium salts (yield: 88 % vs. 60 %).

Keywords: biomass conversion; biorefinery; decomposition; platform chemicals; stabilization.