Glucaric acid lactones

Lactone Methyl ester Methyl glucoside Methyl glucoside-methyl ester Methyl glucoside-lactone Glucaric acid Lactone... 

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

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). 

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... 

Treatment of D-glucaric acid (86) with acidic methanol gives a mixture of dimethyl D-glucarate (90), methyl D-glucarate-1,4-lactone (91), methyl D-glucarate-6,3-lactone (92), and thorough drying under vacuum, led to dilactone 93. The equilibria between the various species were studied in both acidic and basic methanol.265... 

L. Chen and D. E. Kiely, D-glucaric acid esters/lactones used in condensation polymerisation to produce hydroxylated nylons, a qualitative equilibrium study in acidic and basic conditions, J. Carbohydr. Chem., 13 (1994) 585-601. 

The oxidation and subsequent hydrolysis of starch to a-D-glucofuran-urono-6,3-lactone has been studied nitric acid alone, or in combination with nitrites, and nitrogen dioxide, have been examined as oxidants. Good results were obtained for oxidations with nitric acid in the presence of formic acid. A number of patents have been issued on these topics (Ref. 1, pp. 1137, 1138). Treatment of methyl /1-D-glucopyranoside with liquid nitrogen dioxide for 5 h at 12 °C afforded mostly D-glucaric acid, and three isomeric hexopyranosiduloses accounted for an additional 6% of the products.119... 

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

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.

Typically, condensations to polyamide (II), are carried out between an activated, i.e., esterified (diester, ester/lactone, dilactone) form of the aldaric acid (I), and a primary diamine in a polar protic solvent such as methanol at room temperature. Under those conditions any starting single ester form of a five or six carbon aldaric acid is rapidly converted to an equilibrium mixture of acyclic diester and ester/lactone forms. Dilactone, if formed at all, is present in only small amounts. The starting monomer esterified form(s) of the aldaric acid differ from one acid to an other. For example, the monomers of choice for L-tartaric acid (1) and weso-galactaric acid (4) are simple diesters, while for D-glucaric acid suitable monomers are ester/lactones, dilactone, or even the entire alcohol esterified mixture (10). Xylaric acid is also conveniently polymerized as its esterification mixture while the D-mannaric acid monomer is the 1,4 6,3-dilactone (13a). 

PRACTICE PROBLEM 22.8 D-Glucaric acid undergoes lactonization to yield two different y-lactones. What are their... 

The procedure Fischer used for interchanging the ends of the (-l-)-glucose chain began with one of the y-lactones of D-glucaric acid (see Practice Problem 22.8) and was carried out as follows ... 

Fischer actually had to subject both y-lactones of D-glucaric acid (Practice Problem 22.8) PRACTICE PROBLEM 22.18 to the procedure just outlined. What product does the other y-lactone yield ... 

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