Glucaric acid, Glucarate

D-Glucaric acid (41%) Like aldonic acids, aldaiic acids exist mainly as lactones. 

Monosaccharides can be oxidized enzymatically at C-6, yielding uronic acids, such as D-glucuronic and L-iduronic acids (Figure 7.10). L-Iduronic acid is similar to D-glucuronic acid, except for having an opposite configuration at C-5. Oxidation at both C-1 and C-6 produces aldaric acids, such as D-glucaric... 

D-Allaric acid has a symmetry plane and is a meso compound, but o-glucaric acid is chiral. 

L-Altraric acid D-Glucaric acid L-g/ycero-D-ga/acto-Heptaric acid... 

Some OC pesticides can induce the hepatic microsomal enzyme system (Kay, 1970). Tests measuring functions related to these enzymes, such as f.i. D-glucaric acid and 6-b-hydroxicortisol excretion in urine, can be applied to monitor occupational OC exposure. 

Deamination of 2-amino-2-deoxy-D-idonolactone (27) with nitrous acid led, after oxidation with nitric acid, to 2,5-anhydro-D-glucaric acid39,42 (28). As deamination of 2-amino-2-deoxy-D-idonic acid, followed by oxidation, gave 2,5-anhydro-D-idaric acid, the different behavior of the lactone 27 must be due to an attack on the incipient carbonium-ion at C-2 by a favorably disposed hydroxyl group in the molecule, such as at C-5. 

Anti-12-hydroxyendrin and 12-ketoendrin were detected in the feces of pesticide manufacturing workers and its glucuronide conjugate and 12-ketoendrin have been detected in the urine (Baldwin and Hutson 1980). In another study, the levels of anti-12-hydroxyendrin increased accompanied by a sharp rise in D-glucaric acid levels in 29 workers after 7 days of exposure (Ottevanger and Van Sittert 1979 Vrij-Standhardt et al. 1979). 

Changes in the urinary excretion of D-glucaric acid and decreased serum levels of p,p DDE (dichloro-diphenyl dichloroethene a metabolite of DDT) observed in endrin workers were interpreted to signify induction of hepatic enzymes responsible for the metabolism of endogenous and exogenous chemicals (Hunter etal. 1972). 

Vrij-Standhardt WG, Strik JJ, Ottevanger CF. 1979. Urinary D-glucaric acid and urinary total porphyrin excretion in workers exposed to endrin. In Strik JJ, Koeman JH, eds. Chemical porphyria in man. Amsterdam Elsevier/North Holland Biomedical Press, 113-121. 

Urinary D-glucaric acid levels have been shown to be a sensitive indicator of microsomal enzyme induction in workers exposed to chlordecone (Guzelian 1985). However, other substances such as barbiturates, phenytoin, chlorbutanol, aminopyrine, phenylbutazone, and contraceptive steroids as well as other organochlorinated pesticides also cause microsomal enzyme induction and cause changes in urinary D-glucaric acid (Morgan and Roan 1974). 

Yang W, Yan J, Fang H et al (2003) The first fluorescent sensor for D-glucarate based on the cooperative action of boronic acid and guanidinium groups. Chem Commun 792-793... 

Glucuronic acid Gluconic acid 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). 

Mehltretter, C. L. D-Glucaric acid. Methods Carbohydr. Chem., 1963, 2, 46-48. 

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