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

Abstract

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.

Evolution Process and Controlled Synthesis of Humins with 5‐Hydroxymethylfurfural (HMF) as Model Molecule

“…[11a] Ananikov and co-workers proposed higher-molecular-weight compounds of acetalization with three to ten furan cores during HMFa ging in the presence of acidic impurities based on MS/MS data. [14] In our system, simple acetalizationi ntermediates of HMF were not detected by MS/MS. However,t he intermediate 6 was proposed to be the acetalizationp roduct of HMF levulinate, verifying that acetalization can proceed under acidic catalysis.…”

“…In fact, the etherification of HMF into OBMF occurredv ery easily under acidic condition. Galkin et al [14] discovered the presence of OBMF during storage of HMF and ascribed it to acidic impurities.B esides OBMF,t he 1 HNMR spectrum shows the presence of LA andf ormic acid, which are usually obtained at highert emperature ( Figure S1 in the Supporting Information). Similart oO BMF,t he content of LA and formica cid in samples stored at 20 8Cwas higher than at 4 8C.…”

Diamines for Polymer Materials via Direct Amination of Lipid‐ and Lignocellulose‐based Alcohols with NH3

“…These furan-based molecules can be susceptible to various side reactions, especially at the reactiont emperatures required for the amination. [49,52] In view of as traightforward and efficient process, the combined reductive amination-alcohol amination of 5-HMFw as studied. [36,49] In general, it is ah ighly reactive amine, which is advantageous for low temperature curing.…”

Sustainable Utilization of Biomass Refinery Wastes for Accessing Activated Carbons and Supercapacitor Electrode Materials

“…[4,5] Cellulose and various C 6 carbohydrates constitute approximately 75 %o fb iomass. One of the most rapidly developing strategies applied to biomass conversion involves catalytic conversion of carbohydratesi nto 5-hydroxymethylfurfural (HMF) and/orl evulinic acid (LA) and formic acid [1,[5][6][7][8] (Scheme 1). One of the most rapidly developing strategies applied to biomass conversion involves catalytic conversion of carbohydratesi nto 5-hydroxymethylfurfural (HMF) and/orl evulinic acid (LA) and formic acid [1,[5][6][7][8] (Scheme 1).…”