Glucaric acid structure

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... 

These crystal-structure analyses are concerned with the following molecules o-D-glucopyranose monohydrate/ D-xylopyranose/ methyl yS-D-xylopyranoside, di-jS-n-fructopyranose-strontium chloride trihydrate, cellobiose (independent determination), D-glucaric acid, D-galactonic acid, methyl a-D-lyxofuranoside, /3-D-lyxopyranose, methyl 3,4,6-tri-0 - acetyl - 2 - (chloromercuri) - 2 - deoxy - j3 - d - glucopyranoside, D-glu-copyranosyl (potassium sodium phosphate) tetrahydrate," and methyl 6-bromo-6-deoxy-a-D-galactopyranoside. ... 

Calcium carbonate in suspension in glycerol and hydrogen peroxide causes a considerable structural alteration, with the appearance of formaldehyde, formic acid, glyceric acid, and hydroxymalonic acid. Under identical conditions, D-glucose gives formaldehyde, formic acid, acetic acid, oxalic acid, D-glucaric acid, and other, unidentified, hydroxy acids. ... 

It was synthesized by Reichstein (1930a) by dry distillation of saccharic (glucaric) acid in presence of furfurylamine, a synthesis considered as equivocal by Gianturco et al. (1964a) who nevertheless confirmed the structure by elemental analysis, retention time, MS and IR spectra. 

Figure 4.2.2 Top Fischer projections of a few common glycitols and glyconic acids. Note the symmetrical structure of D-mannitol. Bottom Molecular structures of (a) linear D-mannitol, (b) bent D-glucitol, (c) D-glucaric acid, and (d) crystal structure of water-in-soluble D-galactaric acid. In the latter structure the intermolecular hydrogen band pattern is indicated.

Styron S.D., French A.D., Friedrich J.D., Lake C.H., Kiely D.E., MM3(96) Conformational analysis of D-glucaramide and X-ray crystal structures of three D-glucaric acid derivatives-Models for synthetic poly(alkylene D-glucaramides), J. Carbohyd. Chem., 21, 2002,27-51. 

Structure. Hydrolysis of methylated melibionic acid gives 2,3,4,5-tetra-0-methyl-D-gluconic acid (identified by failure to form a lactone, and by nitric acid oxidation to tetra-O-methyl-D-glucaric acid) and 2,3,4,6-tetra-0-methyl-D-galactose (identical with the product obtained by hydrolysis of... 

The problem now resolved into determining the configuration of C-4 for structures H and J (reaction 2.5). Fischer reasoned that because both D-glucaric acid and D-mannaric acid were optically active, the configuration of the OH group at C-4 had to be to the right (structure K below) because, if it were to the left, the aric acid of structure H would be optically inactive due to intramolecular symmetry (structure L, below). 

Fischer contemplated the problem and reasoned that D-glucaric acid could be obtained by nitric acid oxidation of two different hexoses, structure M above... 

Fischer confirmed the structures by synthesizing L-gulose and showing that its oxidation with nitric acid did indeed give D-glucaric acid, the same compound that was obtained by oxidizing D-glucose [4]. This also meant that the structure for D-arabinose was Q and D-fructose was R, shown below ... 

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