Hydroxymethylfurfural from fructose

Roman-Leshkov, Y., Chheda, J. N., and Dumesic, J.A. (2006). Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science, 312, 1933-1937. 

Torres, A. I., Daoutidis, P., and Tsapatsis, M. (2010). Continuous production of 5-hydroxymethylfurfural from fructose a design case study. Energy Environ. Sci, 3, 1560-1572. 

Synthesis of 5-Hydroxymethylfurfural from Fructose and Glucose Using Heterogeneous Catalysts... 

I. 210 but sometimes exceeds 1.235. The juice yield is very low (250-300 I/tonne) and only vertical hydraulic presses are capable of extraction. The resulting juice is extremely viscous and dark, with pronounced grape aromas. The Pedro Ximenez variety is particularly rich in organic acids. The heat of the Andalusian sun provokes the formation of a significant quantity (50-75 mg/1) of hydroxymethylfurfural from fructose. 

Kroger, M., Prusse, U., and Vorlop, K. D., A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose. Topics Catalysis 2000, 13 (3), 237-242. 

It has often been proclaimed that 5-hydroxymethylfurfural (HMF, Fig. 8.35) could be an ideal cross-over compound between carbohydrates and petrochemistry [184], as it is a bifunctional heteroaromatic compound that is accessible from fructose in one step. It was expected that HMF could be developed into a valuable synthetic building block and that its derivatives, such as furan-2,5-dicarb-oxylic acid (FDA), would be able to compete with fossil-derived monomers for use in thermostable polyesters and polyamides. 

Yong G, Zhang Y, Ying JY (2008) Efficient catal5fric system for the selective production of 5-hydroxymethylfurfural from glucose and fructose. Angew Chem Int Ed 47 9345-9348... 

A fully bio-based polyester beverage bottle was subsequently developed (lab scale) by PepsiCo. Coca-Cola is also pursuing a 1(X)% bio-based bottle. TPA can also be derived from bio-derived intermediates such as bio-xylene or from bio-derived 5-hydroxymethylfurfural or furandicarboxylic acid [EDCA] from fructose via alk-oxymethyl fufural. Efforts to synthesize bio-TPA via the muconic acid route without going via p-xylene are also under development. ... 

Hydroxymethylfurfural from Glucose and Fructose. Angewandte Chemie International Edition 2008,47 (48), 9345-9348. 

FIGURE 15.8 Biosynthetic pathway of synthesis of hydroxymethylfurfural (5-HMF) from fructose. 

The dehydration of fructose 40 or glucose into 5-hydroxymethylfurfural 41 is a process which has been exploited to convert biomass into higher value products. The reaction has been achieved using a chromium NHC complex, formed in situ from CrCl and the NHC 42 (Scheme 11.10) [16], The reaction is performed in the ionic liquid BMIM+Cl (l-butyl-3-methylimidazolium chloride). 

Heterogeneous catalysts, particularly zeolites, have been found suitable for performing transformations of biomass carbohydrates for the production of fine and specialty chemicals.123 From these catalytic routes, the hydrolysis of abundant biomass saccharides, such as cellulose or sucrose, is of particular interest. The latter disaccharide constitutes one of the main renewable raw materials employed for the production of biobased products, notably food additives and pharmaceuticals.124 Hydrolysis of sucrose leads to a 1 1 mixture of glucose and fructose, termed invert sugar and, depending on the reaction conditions, the subsequent formation of 5-hydroxymethylfurfural (HMF) as a by-product resulting from dehydration of fructose. HMF is a versatile intermediate used in industry, and can be derivatized to yield a number of polymerizable furanoid monomers. In particular, HMF has been used in the manufacture of special phenolic resins.125... 

Hydroxymethylfurfural is produced by the action of oxalic acid, at a high temperature and under pressure, on either fructose or glucose, although it is more readily obtained from the ketose. No hydroxy-... 

In addition to enzymatic hydrolysis (see Section 5.8.1), inulin can be hydrolyzed chemically and subsequently dehydrated to yield hydroxymethylfurfural (van Dam et al., 1986), a key industrial chemical (Gretz et al., 1993 Fuchs, 1987 Kunz, 1993 Makkee et al., 1985 van Dam et al., 1986). Likewise, catalytic hydrogenation of D-fructose yields D-mannitol and D-sorbitol mixtures from which mannitol can be removed via crystallization (Fuchs, 1987). 

Hydroxymethylfurfural (HMF), a promising intermediate for chemical production [140], can be produced from glucose (Scheme 1) and fructose by dehydration. Conversion of fructose to HMF using l-H-3-methylimidazolium chloride as both catalyst and solvent was reported to result in 92% yield after only 45 min [141], The conversion of the more abundant substrate, glucose, often results in poor selectivity, but it was successfully converted with 70% yield using a chromium(II) chloride catalyst in [C2mim][Cl] [142, 143], The patented method includes monosaccharides, disaccharides and polysaccharides as substrates [143],... 

Increasing attention has recently been devoted to the selective dehydration of hexoses, particularly fructose, to 5-hydroxymethylfurfural (10, Scheme 8) [14], This compound, which can thus be derived from renewable biomass and agricultural surpluses, finds application as starting material in the preparation of fine chemicals and polymers. 

Furfural and thence furan, by vapour phase decarbonylation, are available in bulk and represent the starting points for many furan syntheses. The aldehyde is manufactured from xylose, obtained in turn from pentosans which are polysaccharides extracted from many plants, e.g. corn cobs and rice husks. Acid catalyses the overall loss of three moles of water in very good yield. The precise order of events in the multistep process is not known for certain, however a reasonable sequence is shown below. Comparable dehydrative ring closure of fructose produces 5-hydroxymethylfurfural. 

As furan derivatives, both furfural and 5-hydroxymethylfurfural (HMF) are readily prepared from renewable biomass. Furfural can be easily obtained from a variety of biomass containing pentoses, mainly including com cobs, oats and rice hulls, sugar cane bagasses, cotton seeds, ohve husks and stones, and wood chips. Furfuryl was first produced in the early nineteenth century and right now the annual production is 300,000 tons [101]. On the other hand, HMF is another major promising furan derivative due to its rich chemistry and potential availability from hexose carbohydrates or from their precursors such as fructose, glucose, sucrose, cellulose, and inulin [14]. 

Ketohexoses react with acids much more rapidly than aldohexoses and, hence, give better yields of 5-hydroxymethylfurfural. The reaction proceeds at an appreciable rate in aqueous solutions of fructose, and even glucose, at 100 to 150° without added acids. Since furfurals readily undergo further reactions with the formation of brown-colored products, it is probable that many of the brown colors produced in food processing and in autoclaved solutions result from the intermediary formation of furfurals (60). (See also p. 446). When concentrated hydrochloric or hydrobromic acid is used, the corresponding 5-halogenomethylfurfural is produced. 

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