Glucosone d-, 2-

D-Glucosone (XII), prepared from D-glucose phenylosazone (XI) by the action of concentrated hydrochloric acid, is treated in aqueous solution with potassium cyanide. The imino-D-glucoascorbic acid (XIV) which readily separates shows many of the properties of ascorbic acid. Thus it shows a strong selective absorption band in the ultra-... 

Although no D-glucosone was obtained by the action of formaldehyde on D-glucose phenylosazone,19 Briill28 successfully decomposed the osazone with an excess of pyruvic acid. An improved procedure has been described, and the decomposition of D-glucose phenylosazone with glyoxal has been reported.18... 

Partially methylated derivatives of D-glucosone have been prepared by decomposition of the corresponding partially methylated phenylosazones with p-nitrobenzaldehyde osones have been obtained from 5-0-methyl-D-glucose phenylosazone and from 3,4,5-tri-O-methyl-D-glucose phenylosazone in this way.22 Although 6-0-methyl-D-glucose phenylosazone is not altered by heating with benzaldehyde or piperonal in aqueous ethanolic... 

Evans, Nicoll, Strause and Waring46 oxidized D-glucose and D-fructose in aqueous solution with excess cupric acetate at 50° for the purpose of ascertaining whether the general principles underlying the mechanism of carbohydrate oxidation in alkaline solutions are sufficient to explain the course of such oxidations in acid solutions. D-Glucosone was claimed to be one of the first products of oxidation the osone was not isolated, and,... 

Weidenhagen48 further investigated this reaction he found that osone formation could become the main reaction if ethanol or methanol was used as a solvent, the cupric acetate was not in excess, and the reaction time was limited. Oxidation of D-glucose or D-fructose was reported to give a 40% yield of D-glucosone.14-46... 

Following a report60 that D-fructose, but not D-glucose, is oxidized by selenious acid, Dixon and Harrison61 used this reagent to prepare D-glucosone from D-fructose in aqueous solution isolation and purification were carried out after the manner of Fischer,4 but no yield was given. By this... 

Bayne, Fewster and Mitchell16 prepared VII by the method of Stacey and Turton, and recorded physical properties closely agreeing with those reported by Maurer.66 The compound was clearly related to D-glucosone, prepared from D-glucose phenylosazone and by direct oxidation, since, on treatment with dry acetone containing concentrated sulfuric acid, it gave crystalline tri-0-isopropylidene-(2-hydroxy-D-arabmo-hexose). 7... 

The preparation of sirupy 1-methyl-D-glucosone and crystalline 1-phenyl-D-glucosone (XXII), via the corresponding 2,3 4,5-di-0-isopropylidene derivatives, by Ohle and his colleagues61 64 (by treatment of 2,3 4,5-di-O-isopropylidene-2-oxo-D-arabmo-hexonic acid (XXI) with the requisite... 

In the preparation of D-glucosone by the direct oxidation of D-glucose, D-fructose, or D-mannose by such reagents as that of Fenton,37 cupric acetate,16- 46- 46 selenious acid,16-61 etc., the degree of oxidation must be carefully controlled if the osone, which is the first product, is to be the main product of the reaction. The nature and mechanism of formation of the products of further oxidation of D-glucosone are discussed on p. 68. 

The reaction mechanism postulated by Wolfrom, Schuetz and Cavalieri87 for the formation of 5-(hydroxymethyl)-2-furaldehyde from D-glucose involves the enol (XXXV) of 3-deoxy-D-glucosone as an intermediate an alternative pathway proposed by these same workers included the enol... 

XXXV), 3-deoxy-D-glucosone itself, and 3,4-dideoxy-D-glucosone-3,4-ene... 

Neither of these reports has been confirmed, and, in both cases, evidence for the production of D-glucosone is incomplete, being based mainly on the preparation of non-definitive derivatives. These results are discussed more fully in the Section dealing with the biological significance of the osones. 

El Khadem18 reported that D-glucosone gives a single spot when developed with collidine-water or phenol-water, Rp values of 0.21 and 0.13 respectively, being recorded. It was stated18 that no movement of the osone occurs on development with butanol saturated with water. Homo-... 

Biologically formed D-glucosone phosphate has been separated from d-glucosone by paper chromatography, using ethyl acetate-amyl alcohol-formamide (1 2 3) as developer. This solvent mixture does not completely separate D-glucosone phosphate from D-glucose 6-phosphate and D-fructose 1-phosphate.16... 

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