The preparation of 5‐hydroxymethylfurfuraldehyde from high fructose corn syrup and other carbohydrates

Abstract

5‐Hydroxymethylfurfuraldehyde (HMF) was prepared from high fructose corn syrup (HFCS), or crystalline D‐fructose, in high yield and purity. A 95–97% conversion of fructose to HMF was achieved using 25 mol% (based on fructose) boron trifluoride etherate catalyst in dimethyl sulphoxide, under a nitrogen atmosphere, a reaction temperature of 273 K and 30 min reaction time. Inferior yields of HMF were obtained from glucose and starch.

Expanding the Limits of Organoboron Chemistry: Synthesis of Functionalized Arylboronates

“…26, 65 Similarly, results from theoretical calculations reinforce the conclusion that cyclic reaction pathways are dominant for HMF formation from glucose and xylose 27. While selectivity in the presence of water is low, high yields (>90 %) can be achieved in aprotic solvents such as DMSO 66. Previous studies suggest that fructose is predominantly present in the furanose form in aprotic solvents such as DMSO and at higher temperatures, when compared to the dominant β‐pyranose form in pure water 31–33.…”

“…However, a strong incentive exists for the development of processes that utilize cheap and abundantly available glucose directly, without requiring an additional step of glucose isomerization to fructose. In pure water, glucose dehydration to HMF is nonselective (about 6 %),69 and importantly the yields of HMF in aprotic polar solvents such as DMSO are low (≈42 %) even for a 3 wt % glucose solution 66. In this respect, the yield to HMF using the above‐mentioned biphasic reactor system to process 10 wt % glucose feed solution can be improved by increasing the DMSO content to 60 wt % in the aqueous phase and using a 7:3 (w/w) mixture of MIBK/2‐butanol as the extracting solvent.…”

Exploring the Oxidative Cyclization of Substituted N‐Aryl Enamines: Pd‐Catalyzed Formation of Indoles from Anilines

“…26, 65 Auch theoretische Ergebnisse stützen den Befund, dass die HMF‐Bildung aus Glucose und Xylose hauptsächlich über cyclische Intermediate verläuft 27. Während in Gegenwart von Wasser die Selektivität nur gering ist, lassen sich in aprotischen Lösungsmitteln wie Dimethylsulfoxid (DMSO) hohe Ausbeuten (>90 %) erzielen 66. Nach früheren Arbeiten liegt Fructose in aprotischen Lösungsmitteln wie DMSO und bei höheren Temperaturen in der Furanoseform vor, während in Wasser die β‐Pyranoseform vorherrscht 31–33.…”

Selective dehydration of fructose and sucrose to 5‐hydroxymethyl‐2‐furfural with heterogeneous ge (IV) catalysts

“…Many efforts are devoted to the dehydration of sugars to 5-hydroxymethyl-2furfural (HMF), one of the most versatile and important building blocks in biofuel chemistry [4][5][6][7][8][9]. Typically, the homogeneous catalysts such as mineral acids [10,11], Lewis acids [12,13], and metal chlorides [14][15][16][17] have been used in the selective dehydration of fructose and sucrose to produce HMF at present. For example, Zhao et al [14] reported that a HMF yield of 83% was obtained with CrCl 2 as the catalyst in 1ethyl-3-methylimida-zolium chloride ([EMIM][Cl]) at 80 C for 3 h. Yong et al [15] studied the production of HMF from fructose in 1-butyl-3-methyl imidazolium chloride ([BMIM][Cl]) using CrCl 2 as catalyst, and a 96% yield of HMF was achieved at 100 C for 6 h. Moreover, Hu et al [16] found that SnCl 4 could efficiently convert sucrose to HMF in 1-butyl-3methylimidazoliumtetrafluoroborate ([BMIM]BF 4 ) and the product yield was as high as 65%.…”