Turanose, phenylosotriazole

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). 

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. 

---