Glucose glucaric acid

Figure 9.11 Oxidation products of glucose. Gluconic acid is an aldonic acid formed when the aldehyde group is oxidized. Glucuronic acid, a uronic acid, is a result of oxidation of the primary alcohol group. When both the aldehyde and the primary alcohol groups are oxidized, glucaric acid is formed, which is an aldaric acid.

D-Glucaric acid, directly produced by nitric oxidation of glucose or starch, is usually isolated as its 1,4-lactone. The technical barrier to its large-scale production mainly includes development of an efficient and selective oxidation technology to eliminate the need for nitric acid as the oxidant. Because it represents a tetrahydroxy-adipic acid, D-glucaric acid is of similar utility as adipic acid for the generation of polyesters and polyamides (see later in this chapter). 

D-glucose D-gluconic acid D-glucaric acid D-glucitol... 

The nitrous acid deamination of 2-amino-2-deoxy-D-mannose (8), in the favored conformation, the amino group ofwhich is axially attached, leads, in contrast, uniquely to D-glucose,15 characterized, after oxidation by nitric acid, as D-glucaric acid (9). This result has also been verified by direct crystallization of the D-glucose and by assay with D-glucose oxidase.44"... 

Problem 22.27 Fischer prepared L-gulose by oxidizing o-glucose to two separable lactones of glucaric acid. These were reduced to lactones of gluconic acid, which were further reduced. Give all the structures in these... 

The carboxylic acids derived from glucose are therefore gluconic acid, glucuronic acid, and glucaric acid. 

Although glucose has some of the properties expected of an aldehyde, it lacks others. For example, it forms certain carbonyl derivatives (e.g., oxime and cyanohydrin), and can be reduced to the hexahydroxyhexane (sorbitol), and oxidized with bromine to gluconic acid (a monocarboxylic acid). (With nitric acid, oxidation proceeds further to give the dicarboxylic acid, D-glucaric acid.)... 

D-Glucaric acid is readily prepared by oxidation of D-glucose or starch with nitric acid, as described by Bose et al.,252 who also developed a... 

The carbonyl functionality at Cl and the primary hydroxyl group at C6 of D-glucose are readily oxidized/reduced to yield D-fucose, D-glucaric acid, D-glucitol,... 

Glucaric acid Starch, glucose Lactone, polyglucaric ester, polyglucaric amide Werpy and Petersen, 2004... 

Finally, oxidation experiments on D-gluconic and D-gulonic acid produced the head-to-tail enantiomers D/L-glucaric acid. Thus, it was apparent that these acids could only be derived from D-glucose and D-gulose. In a seminal report published in 1891, Fischer... 

More recently, Bonfatti et al. (1999) have verified that the reactivity of glucose at Ti/Pt electrodes was acceptable in all current densities, slightly higher at 600A m-2 however, the electrochemical mineralization was low, particularly over a long electrolysis time, due to the accumulation of intermediates, mainly glucaric acid, which resisted further attack at the platinum electrode. The situation improved by increasing the temperature to 56°C. 

Fig. 2 -23. Oxidation of D-glucose (1) to D-gluconic acid (2) and o-glucaric acid (3). The free acids occur mainly as corresponding lactones.

Both the aldehyde and 1° alcohol of an aldose are oxidized to carboxy groups by treatment with warm nitric acid, forming an aldaric acid. Under these conditions, D-glucose is converted to D-glucaric acid. 

Because aldaric acids have identical functional groups on both terminal carbons, some aldaric acids contain a plane of symmetry, making them achiral molecules. For example, oxidation of D-allose forms an achiral, optically inactive aldaric acid. This contrasts with D-glucaric acid formed from glucose, which has no plane of symmetry, and is thus still optically active. 

Aldaric acid (Saccharic acid) 6 Glucaric acid Oxidation product of glucose... 

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