6-deoxy phenylosazone

Diels and Stephan173 treated the benzoate of 3-hydroxy-2-butanone with bromine, and obtained crystalline 1-bromo- and 1,1-dibromo- derivatives. With dilute alkali, these formed 4-deoxy-DL-gZycero-tetrulose and 4-deoxy-DL-erythrosone respectively. Both compounds gave with phenylhydrazine 4-deoxy-DL-erythrose phenylosazone, which had previously been prepared from the corresponding aldotetrose.174... 

Because the phenylosazone and tetrahydroxybutylquinoxaline derivatives of D-glucosone have been isolated from 1-deoxy-l-p-toluidino-D-fruc-tose in high yields, 1,2-enolization of the aminodeoxyketose must predominate over 2,3-enolization. No proof for 2,3-enolization is known at present. The sequence of reactions (in alkali) which lead from the aminodeoxyketose (XVI) through the 1,2-enediol (XVIII) to the glycosone (XIX) are thought to be as follows ... 

Finally, the mutarotation of tetra-O-acetyl-n-arohfno-hexose phenylosa-zone, of 4-deoxy-L-ffZyccro-tetrose phenylosazone, and of tetra-O-acetyl-D-lyxo-hexose phenylosazone can in no way be explained by cyclization, since in these cases there is definitely no possibility for ring formation to take place. 

Tetrulose, h-glycero-, phenylosazone, 148 Thioaldonic acids, phenylhydrazides, 165 Thiogalaotonic acid, d-, phenylhydra-zide, 118-120, 122 Threaric acid, dl-, 178 Threonic acid, dl-, 179 —, 4-chloro-4-deoxy-DL-, 179 —, (-)-4-deoxy-, 180 —, 4-deoxy-D-, 171, 181 —, 4-deoxy-DL-, 180 —, 4-deoxy-L-, 171 Tragacanthin, 272, 279 Transformations, of carbohydrates, 65 Trehalose, 323... 

The isolation of D-aroWno-hexulose phenylosazone from both 1,4-anhydro-D-mannitol and 1,5-anhydro-D-glucitol indicates that o-aroMno-hexosulose is among the reaction products. - Crude methyl D-glucofurano-sides in dilute sulfuric acid yield pyruvaldehyde, and 2-amino-2-deoxy-D-glucose hydrochloride suffers oxidative deamination. ... 

The glycosulos-3-enes are theoretically derived from a 3-deoxyglycosulose by the loss of one molecule of water per molecule. A compound of this type, (32), was first isolated as the phenylosazone by Wolfrom, Wallace, and Metcalf, and was shown to be an intermediate in the conversion of 1-deoxy-tetra-O-methyl-D-orobtno-hexopyranos-l-ene (31) (tetra-O-methyl-n-glucoseen-1,2) to 5-(methoxymethyl)-2-furaldehyde (33). The evidence... 

Fischer reduced n-arabmo-hexulose phenylosazone (43) with zinc and acetic acid, and obtained l-amino-l-deoxy-n-fructose (62) ( isoglucosamine ) as its crystalline acetate. He used this reaction as a means of... 

By the catalytic reduction of the phenylosazone from lactose, Kuhn and Kirschenlohr obtained both /3-n-gaIactopyranosyl-(l— 4)-l-amino-l-deoxy-D-fructose and /S-n-galactopyranosyl- (1- -4) -2-amino-2-deoxy-D-glu-cose. The A -acetyl derivative of the latter was found to be identical with a disaccharide obtained from the partial hydrolysis of a blood-group substance. The structure of a disaccharide obtained from the partial hydrolysis of heparin was likewise confirmed by comparison of the disaccharide with a synthetic product obtained by catalytic hydrogenation of the osazone from maltose. - Here, too, both the 1-amino-l-deoxy and the 2-amino-2-deoxy compounds were obtained. 

---