4- O-Methyl-glucuronic acid

The NMR spectrum of the dry sample showed broad unresolved peaks that correspond to a typical mixture of 4-O-methyl-D-glucuronic acid, L-arabinose and D-xylose, and proteins (Oliveira et al., 2010) (Figure 5). 

The second important group of hemicelluloses found in softwoods are the arabino-(4-0-methylglucurono)xylans, which may make up from 5 to 10% of the dry weight of the wood. These consist of /3-1,4-linked D-xylopyranose units, partially substituted by L-arabino-furanose (at the 3 position) and by 4-O-methyl D-glucuronic acid (at the 2 position). The frequency of these substituent groups is around 1 to 2 residues per 10 xylose units. 

Xyloisosaccharinic acid [2,4-dihydroxy-2-(hydroxymethyl)butanoic acid] is one of the major, alkaline-degradation products of wood xylan, in particular, that of birch. The disaccharide, 2-O-D-xylopyranosyl-L-arabinose, which was isolated as a hydrolysis product of corn-cob hemicellulose, is readily degraded at 100° in 15 mM Ca(OH)2 to acidic products, primarily saccharinic acids. Xylan oligosaccharides from corn-cob hemicellulose produced 2,4-dihydroxy-2-(hydroxymethyl)buta-noic acid when exposed to 0.02 M Ca(OH)2 at 25°. However, it was noted that the xylan, itself, was stable at 100° in Af NaOH. The major acidic component of the hemicellulose fraction of slash pine Pinus el-liotti) after acid hydrolysis was identified as 4-O-methyl-D-glucuronic... 

Xylans are the major hemicelluloses of many plant materials, where they often contribute to the rigidity of plant cell walls. Most xylans are heteropolysaccharides with a homopolymeric backbone chain of 1,4-linked j8-D-xylo-pyranose units. The degree and t pe of substitution of the backbone is dependent on the plant origin of a xylan. In addition to xylose, xylans may contain L-arabinose, D-glucuronic acid or its 4-O-methyl ether, and acetic, p-coumaric, and ferulic acids. 

Both D-glucuronic acid and/or its 4-O-methyl ether and arabinose are also present in cereal xylans (4). Endospermic arabinoxylans of annual plants, often referred to as pentosans, are because of their branched structures more soluble in water and dilute alkali than xylans of lignocellulosic materials. They also have at least one, or even two, substituents per xylose residue (5). 

In concentrated sulfuric acid, D-glucuronic acid is dehydrated more slowly than either its 4-O-methyl derivative or D-glucose, probably because of the stability of its lactone. All hexuronic acids, however, eventually produce the same characteristic absorbance that corresponds roughly to a composite of 5-formyl-2-furoic acid, 2-furaldehyde, and reductic acid. It is interesting that a thin-layer chromatographic examination of the reaction products of D-glucuronic acid with 89% sulfuric acid at 70° revealed 5-formyl-2-furoic acid as a major product, but no evidence was obtained for the presence of reductic acid. This result is in distinct contrast to the products obtained in dilute acid solutions, in which 5-formyl-2-furoic acid is produced in very low yield, whereas reductic acid is formed in yields in excess of 10%. 

Rha), arabinose (Ara), galactose (Gal), xylose (Xyl), and 4-O-methyl-glucuronic acid (M-GluU) are the same or larger than after intensive hydrolysis, evidence for a more moderate action of the acid. But for a complete hydrolysis of cellulose and glucomannan, the moderate method is not sufficient therefore, the peaks for mannose (Man) and glucose (Glu) are much smaller after this treatment. 

A. F. Bochkov and Ya. V. Voznyi, Sugar ortho esters. Part 8. Synthesis of 4-O-methyl-D-glucuronic acid derivatives, Carbohydr. Res., 32 (1974) 1-8. 

Among the plant polysaccharides there may be mentioned the hemi-celluloses the most common of these contain 4-O-methyl-D-glucuronic acid as branch units linked to a /3-D-xylan backbone.110 The commercially important gum arabic, a soluble polysaccharide produced by Acacia trees and widely used in foods and pharmaceuticals, also contains glucuronic units.111 D-Glucuronic acid has been found in sulfated complex polysaccharides from brown algae.112... 

A pectic polysaccharide containing D-galacturonic acid and terminal units of 4-O-methyl-D-glucuronic acid, along with L-rhamnose and D-galacto-pyranose, was purified from yellow mustard mucilage.124 Pectins are prevalent... 

Aldaric acids or their derivatives undergo ready epimerization in pyridine. Alkaline treatment of 4-O-methyl-D-glucuronic acid in the presence of air affords 4-O-methyl-D-glucaric and -D-mannaric acids as well as lower O-methylaldaric acids.262 The two diastereo-isomeric 3-deoxy-2-C-(hydroxymethyl)pentaric acids obtained from... 

O-methyl-D-glucuronic acid have also been obtained by treatment of alginates with alkali.263... 

Despite indications (from analytical data) that a monomethyl ether of a uronic acid occurs in the hydrolyzates of several polysaccharides, definite evidence for the presence of 4-O-methyl-D-glucuronic acid did not appear until 1948, when White found it in mesquite-gum hydroly-zate.14 Confirmation of its presence therein has since13 appeared, and it has also been found in the hydrolyzates from gum myrrh,6 aspen wood,14 and Eucalyptus regnans wood.16... 

Conversion of the reducing end-unit in 2-0-(4-0-methyl-D-glucosyl-uronic acid)-D-xylose to a tartronic semialdehyde residue (as in LXXVII) facilitated the ready isolation of 4-O-methyl-D-glucuronic acid by acid hy-... 

Wood xylans are characterized by the presence of residues of 4-O-methyl-D-glucuronic acid linked to position 2 of D-xylose in the main xylan chains (XXVI), and, accordingly, the aldobiouronic acid, 0-(4-0-methyl-a-D-glu-cosyluronic acid)-(l —> 2)-D-xylose (IX), is commonly isolated after the graded hydrolysis of such xylans. Partial acid hydrolysis of Monterey pine wood69 furnishes this compound together with the isomeric aldobiouronic acid, 0-(4-0-methyl-a-n-glucosyluronic acid)-(l—>3)-D-xylose, as a minor product, but the role of the (1 — 3)-linked aldobiouronic acid unit in the... 

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