Critical Influence of 5-Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis

Spectral studies revealed the presence of a specific arrangement of 5‐hydroxymethylfurfural (5‐HMF) molecules in solution as a result of a hydrogen–bonding network, and this arrangement readily facilitates the aging of 5‐HMF. Deterioration of the quality of this platform chemical limits its practical applications, especially in synthesis/pharma areas. The model drug Ranitidine (Zantac®) was synthesized with only 15 % yield starting from 5‐HMF which was isolated and stored as an oil after a biomass conversion process. In contrast, a much higher yield of 65 % was obtained by using 5‐HMF isolated in crystalline state from an optimized biomass conversion process. The molecular mechanisms responsible for 5‐HMF decomposition in solution were established by NMR and ESI‐MS studies. A highly selective synthesis of a 5‐HMF derivative from glucose was achieved using a protecting group at O(6) position. Acting one's age: Aging and decomposition processes of oily 5‐hydroxymethylfurfural (5‐HMF) were evaluated by spectral studies, which revealed the presence of a specific arrangement of 5‐HMF molecules in solution resulting from a hydrogen‐bonding network. Blocking the hydrogen‐bonding network by a suitable protecting group avoided decomposition during the synthesis and facilitated extraction of the product from the reaction mixture.