Phenylosazone

Alekhine had mentioned that turanose reacts with phenylhydrazine. Maquenne prepared the phenylosazone and described its precipitation from water in the flocculent or gel condition that is so very characteristic of the substance, but he did not report an analysis. A year after Ma-quenne s publication, Emil Fischer16 examined a small sample of amorphous turanose which had been sent by Dr. Konowaloff of Moscow. Its phenylosazone was prepared in good crystalline form by several recrystallizations from aqueous alcohol the analysis of these crystals proved conclusively the disaccharide formula for turanose which Alekhine had proposed from the analysis of amorphous substances. The writer had occasion recently to prepare turanose phenylosazone in considerable quantity its very characteristic properties and those of the derived phenylosotriazole are described on pages 27 and 28. 

Twelve years after Fischer s study of turanose phenylosazone there appeared a memoir by Georges Tanret16 which has become the foundation... 

XV. Proof of the Normal Character of the Phenylosazones of Turanose and Maltose... 

It has been assumed in the preceding section that the phenylosazones of turanose, maltose, and D-glucosyl-D-arabinose have structures like that of D-glucose pjienylosazone. This normal osazone structure is now proved40 by the following data for the turanose and maltose osazones, and there can be little doubt that it also holds for the osazone of d-glucosyl-D-arabinose. Turanose phenylosazone has been converted by... 

With an abundant supply of pure crystalline turanose available, its phenylosazone (XIII) could be studied in more detail than had been possible in Fischer s investigation of the small quantity of amorphous turanose that he had received from Konowaloff (p. 9). 

Turanose Phenylosazone. A mixture of 4 g. of turanose, 2 ec. of water, and 1 co. of phenylhydrazine was warmed on the steam-bath until solution was complete. To the cooled solution was added 3.5 cc. of phenylhydrazine and 4 cc. of glacial acetic acid, and the mixture returned to the steam-bath for one hour. At the expiration of this time, 40 cc. of warm 60% alcohol was added and, upon cooling, a rapid crystallization of the osazone occurred. The osazone was recovered by filtration and washed with absolute alcohol followed by ether to yield 4.2 g. (69%) of lemon-yellow needles. The osazone is soluble in hot water and separates on cooling as jelly-like particles, but water is not a satisfactory solvent for its purification. It was recrystallized from 15 parts of 95% alcohol with good recovery, as needles which melted with decomposition at 200-205° and rotated [ ]d +24.5° - +33.0° (24 hours, constant value c, 0.82) in a mixture of 4 parts of pyridine, by volume, and 6 parts of absolute ethyl alcohol. In methyl cellosolve (ethylene glycol monomethyl ether) solution it rotated C< 3d" + 44.3°— + 48.5° (24 hours, constant value c, 0.80). 

Turanose phenylosotriazole, the configurational formula of which is XIV, was prepared from turanose phenylosazone. 

Turanose Phenylosotriazole. A solution of 15 g. of turanose phenylosazone in 300 cc. of hot water was placed on the steam-bath and a solution of 22 g. of copper siilfate pentahydrate in 150 cc. of hot water was added. The mixture turned a deep cherry-red at once and in a short time (fifteen min.) a red precipitate had formed and the solution had become green. After thirty minutes from the time of addition of the copper solution, the solution was cooled, filtered, and the copper removed as sulfide. The clear light yellow filtrate was neutralized with 45 g. of barium carbonate and the insoluble material removed by filtration. The filtrate was extracted with five 50-cc. portions of ether to remove the aniline, and the aqueous portion was concentrated in vacuo to a thick sirup. The sirup was dissolved in 60 cc. of warm alcohol, filtered to remove a slight turbidity and diluted with 65 cc. of ether. Upon cooling and scratching, the product crystallized as large prisms yield 8.9 g. (72%). The phenylosotriazole was recrystallized from 10 parts of alcohol and when pure showed the melting point 193-194° and rotated [a Jj" + 74.5° in aqueous solution (c, 0.90). 

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-... 

The formation of D-glucose phenylosazone from chitosamine showed its relationship to D-glucose and D-mannose and Irvine and Hynd7 succeeded in preparing both D-mannose and D-glucose from chitosamine. 

Methylation was accomplished by direct conversion of the acetyl derivative as previously described. The final product contained 45% OCHs. Molecular weight determinations in benzene gave values representing 18 to 19 D-fructose residues. Hydrolytic products of the methyl derivative were separated by conversion to benzoyl derivatives. The trimethylfructose was identified as 3,4,6-trimethyl-D-fructofuranose by its phenylosazone. The authors conclude that the ratios 1 3 1 exist among the di-, tri-, and tetramethyl-D -fructoses produced by the hydrolysis. 

A micro-diffusion method has been devised by Winnick101 for the determination of acetaldehyde. Procedures for the assay of glycerose were developed by Jayme, Satre and Maris.167,168 They dehydrated glycerose to pyruvic aldehyde by distillation from mineral acid, and determined the pyruvic aldehyde as its phenylosazone. 

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... 

It has recently been reported21 that a mixed osazone of 3,4-di-O-methyl-D-glucose can be converted, by treatment with p-nitrobenzaldehyde, into an osone which reacts with phenylhydrazine to give 3,4-di-O-methyl-D-glucose phenylosazone. Von Lebedev29 claimed to have obtained D-glu-cosone 6-phosphate, isolated as an amorphous lead salt, by the action of hydrochloric acid on the phenylosazone prepared from D-fructose 6-phosphate. 

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