2-Furaldehyde from pentoses

Aso98 first proposed 5-hydroxy-2-oxo-3-pentenal (94) as an intermediate in the conversion of uronic acids to reductic acid,190 191 but this proposal does not appear to have been experimentally tested, although the intermediate was prepared.190 Isbell121 suggested a mechanism in which the formation of reductic acid and 2-furaldehyde from pentoses and uronic acids results from the reaction of different tautomers of 94. Although other mechanisms have been suggested,100 102 115 Isbell s original scheme seems adequate to explain the experimental facts. 

Neher and Lewis177 obtained 2-furaldehyde from 2,3,4-tri-O-methyl-L-arabinose by heating with dilute acid after preliminary enolization with alkali. Isbell83 proposed a mechanism for this conversion similar to that for the conversion of tetra-0-methyl-(2-hydroxy-D-glucal) into 5-(hydroxymethyl)-2-furaldehyde XLIV was suggested as an intermediate. In Hurd and Isenhour s178 scheme for the formation of 2-furaldehyde from free pentose, the enol (XLV) of a 3-deoxypentosone was regarded as an inter-... 

The mechanism of pentose dehydration has been a matter of study for several years. The accepted pathway (see Scheme 1) to 2-furaldehyde from a pentose, in this case D-xylose (1), involves the reversible formation of a 1,2-enediol (2) followed by dehydration to the enolic form (3) of a 3-deoxypentosulose, which is further dehydrated to the 3,4-dideoxypent-3-enos-2-ulose (4) prior to cyclization to afford 2-furaldehyde 5. This mechanism, initially suggested by Isbell,has been substantiated by later work. This confirmation required incorporation of deuterium or tri-tium into the furaldehyde at various ring positions. However, when... 

The formation of such chromones as 3,8-dihydroxy-2-methyl-chromone by treating uronic acids or pentoses with dilute acid was reported by Aso,119 and studied by Popoff and Theander,120 who obtained a number of these compounds in 3.5% yield, as well as some catechols. Although nothing is yet known about the mechanism of formation of these compounds, the fact that the chromones contain 10 carbon atoms and are produced both from pentoses and uronic acids suggests that they may be derived from 2-furaldehyde or re-ductic acid, or produced from a decarboxylated intermediate. 

Ahmad, T., Kenne, L., Olsson, K., and Theander, O., The formation of 2-furaldehyde and formic-acid from pentoses in slightly acidic deuterium-oxide studied by H-l-Nmr spectroscopy. Carbohydrate Res 1995, 276 (2), 309-320. 

Among the other sugars detected in the soil, only the 6-deoxyhexoses have been quantitatively determined. In Delaware soils, rhamnose and fucose, determined by quantitative paper-chromatography, amounted to 20% of the sugars. Under the conditions of furfural formation from pentoses, the 6-deoxyhexoses yield 5-methyl-2-furaldehyde this has been determined by the differential solubilities of the phloroglucides in alcohol. The proportion of 6-deoxyhexoses in some cases exceeded that of pentoses. 

A wide range of carbohydrates is degraded by acids to furan compounds. For example, pentoses give 2-furaldehyde, and hexoses, 5-(hydroxymethyl)-2-furaldehyde (58), which may react further to yield levulinic acid. In 1910, Nef suggested the first mechanism, (55) to (58), for the formation of 5-(hydroxymethyl)-2-furaldehyde. His proposal was made at the end of his classical paper on the saccharinic acids, and was overlooked by subsequent workers and reviewers. In 1944, Haworth and Jones advanced an identical mechanism for the formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose. 

For several years our respective groups have investigated the formation of aromatic compounds from carbohydrates in aqueous solution at various pH-values under reflux or hydrothermolytic conditions. For instance, previous papers(1-6) in this series concerned the degradation of hexoses, pentoses, erythrose, dihydroxyacetone, and hexuronic acids to phenolic and enolic components. Of particular interest were the isolation and identification of catechols, an acetophenone, and chromones from pentoses and hexuronic acids at pH 4.5 (1,2). The formation of these compounds, as well as reductic acid(7),was found to be more pronounced than that of 2-furaldehyde(2) under acidic conditions. 

The aromatic precursors of 4 and 5 were also isolated from these reaction mixtures. This is in contrast to the high yields of 2 obtained from pentoses(8) and hexuronic acids(9) at very low pH. Similar products were obtained in lower yield from glucose and fructose under acidic conditions(10). However, the predominant product of these hexoses was 5-hydroxymethyl-2-furaldehyde (1) as would be expected from prior work( ). Surprisingly, similar products are noted at neutral and even alkaline pH with glucose and... 

Kurata and Sakurai124 have investigated the mechanism of dehydration of L-ascorbic acid by examining the products from it and from L-xyZo-hexulosonic acid after treatment for 1 hour at 100° at pH 2.2, or with 5% sulfuric acid at 100°. In both experiments, 2-furaldehyde and 3-deoxy-L-threo-pentosulose (isolated as the phenylhydrazone) were the major products no pentose was detected. 

Furaldehyde has also been reported as a source of reductic acid,189 and this has been verified.54 The yields are, however, less than 0.5%. D-Xylose also affords small proportions of reductic acid,54,94 but the yields are, apparently, much higher from the other pentoses when they are treated in concentrated sulfuric acid.52... 

The formation of furan derivatives in acid-catalyzed dehydrations of carbohydrate substrates is a well known reaction, first reported by Dobereiner186 in 1832. Among the plethora of compounds formed, 2-furaldehyde is the main product obtained from all of the pentoses, whereas 5-(hydroxymethyl)-2-furaldehyde is the major product... 

The transformation of pentoses and hexoses into 2-furaldehyde and 5-(hydroxymethyl)-2-furaldehyde, respectively, by the action of acids is a well-known reaction. Professor Bognar was long interested in ascertaining whether this reaction is reversible. With both a theoretical and a practical goal, the Bogn r group then synthesized the dl forms of several important monosaccharides (xylose, ribose, and arabinose) from the aforementioned furan derivatives. 

Pentoses have frequently been determined in soils by the furfural-phloro-glucinol method.But phloroglucinol also gives precipitates with a variety of other aldehydes, such as 5-methyl-2-furaldehyde, 5-(hydroxymethyl)-2-furaldehyde, and formaldehyde. Orcinol and aniline acetate are much more specific reagents, and no aldehyde present in the hydrochloric acid distillate from soils has been found to interfere in the furfural determination by the orcinol method. The orcinol and aniline acetate methods give, for various Swiss and Norwegian soils, a pentose anhydride content of 0.5 to 8.5 % of the soil organic matter (see Table III) no corrections were made for the furfural derived from uronic acids. 

There are several classes of compounds formed from rapid pyrolysis of carbohydrates. Besides anhydrosugars, they are carbonyl compounds, furan derivatives, lactones, pyran derivatives, phenols, acids and acid esters, and other compounds. In general, the presence of a substantial quantity of 5-hydroxymethylfuraldehyde in the pyrogram indicates that a hexose is present. Substantial amounts of furaldehyde and the absence of 5-hydroxymethylfuraldehyde in the pyrolysis products indicate the presence of a pentose. However, these markers are not diagnostic for a specific hexose or pentose. 

In contrast to the formation of an osazone from phenylhydrazine and the 2-bromo-2-deoxy-hexoses derived from the adduct of tri-O-acetylglucal with bromine, two isomeric products [jwhich were assigned the D-threo-3,4-diacetoxytetrahydro-2-furaldehyde (p-nitrophenyl)hydrazone structures (21)] were isolated from the reaction between 3,4-di-0-acetyl-2-bromo-2-deoxy-D-tAreo-pentose (20) and (p-nitrophenyl)hydrazine. The... 

Furaldehyde (furfural from Latin for bran) is obtained industrially from plant residues which are rich in pentoses, e.g. bran, by treatment with dilute sulfuric acid followed by steam distillation ... 

Dehydration is one of the important acid-base-catalyzed reactions of carbohydrates. In alkaline media, a deoxyaldosulose is formed from a carbohydrate molecule after one molecule of water has been split oflF this product then usually undergoes an intramolecular, oxidoreductive disproportionation to give the corresponding saccharinic acid in acidic media (with pentoses and hexoses), up to three molecules of water are split oE per molecule, with formation of 2-furaldehyde or 5-(hydroxymethyl )-2-furaldehyde. In many cases, polarography makes possible the monitoring of carbohydrate dehydration and the determination of its final products. 

Table II presents the quantitative results of those components volatile enough for GC analysis. At low pH the furan compounds predominate when both glucose and xylose are exposed to 300 C. This is not unexpected since all pentoses form 2-furaldehyde(2) in high yield when exposed to aqueous acid solution( ). However, the presence of 2 in the glucose reaction mixture is of interest. The major product obtained from hexoses at elevated temperatures and aqueous acid is 5-hydroxymethyl-2-furaldehyde(1) with minor amounts of 2-(hydroxyacetyl)furan(15). The 2-furaldehyde has been detected after acidic treatment of fructose(1 ), glucose(15,17), and is a major component after the thermolysis of cellulose in distilled water( ). One plausible explanation for the formation of 2 may involve loss of formaldehyde(18) from glucose with consequent pentose formation. It should be noted that the pyrolysis of 1 does produce a small amount of 2( ). However, the reaction conditions are sufficiently different to suggest a different mechanism for hydrothermolysis.

In acidic degradation, 1,2-enediol forms from the aldose or ketose after a series of dehydration reactions. If the initial sugar is a hexose, 1,2-enediol is converted to HMF. If it is a pentose, 1,2-enediol is converted to 2-furaldehyde. 3-Deoxyaldose-2-ene, 3-deoxyosulose, and osulos-3-ene are intermediates in the acidic degradation of fructose. The last series of reactions include both fragmentation reactions (flavor production) and polymerization reactions (color production). 

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