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- Title
Origin of 5-Hydroxymethylfurfural Stability in Water/Dimethyl Sulfoxide Mixtures.
- Authors
Tsilomelekis, George; Josephson, Tyler R.; Nikolakis, Vladimiros; Caratzoulas, Stavros
- Abstract
In the present work, we combined vibrational spectroscopy with electronic structure calculations to understand the solvation of HMF in DMSO, water, and DMSO/water mixtures and to provide insights into the observed hindrance of HMF rehydration and aldol condensation reactions if it is dissolved in DMSO/water mixtures. To achieve this goal, the attenuated total reflection FTIR spectra of a wide composition range of binary and ternary mixtures were measured, analyzed, and compared to the findings of ab initio DFT calculations. The effect of solvent on the HMF CO and OH vibrational modes reveals significant differences that are ascribed to different intermolecular interactions between HMF and DMSO or water. We also found that DMSO binds to HMF more strongly than water, and interactions with the HMF hydroxyl group are stronger than those with the HMF carbonyl group. We also showed the preferential solvation of HMF CO groups by DMSO if HMF is dissolved in DMSO/water mixed solvent. Frontier molecular orbital theory was used to examine the influence of the solvent on side reactions. The results show that HMF solvation by DMSO increases its LUMO energy, which reduces its susceptibility to nucleophilic attack and minimizes undesirable hydration and humin-formation reactions. This result, together with the preferential solvation of HMF by DMSO, provide an explanation for the enhanced HMF stability in DMSO/water mixtures observed experimentally.
- Subjects
SULFOXIDES synthesis; SPECTRUM analysis; ALDOL condensation; FOURIER transform infrared spectroscopy; ACOUSTIC vibrations; INTERMOLECULAR forces
- Publication
ChemSusChem, 2014, Vol 7, Issue 1, p117
- ISSN
1864-5631
- Publication type
Article
- DOI
10.1002/cssc.201300786