Osazones, phenyl

The reaction of these aldehydes, derived from periodate oxidation, with carbonyl reagents has also been investigated. Studies 147 148 were made on oxidized laminarin, a (1 —> 3)-linked polysaccharide, in which only the terminal residues had been oxidized. The addition of phenylhydrazine acetate detached the remainder of the terminal residue as glyoxal phenyl-osazone. When the aldehydic compounds derived from the periodate oxidation of raffinose and trehalose818a were reacted with p-nitrophenylhydrazine, the authors were surprised to find that one molecule of oxidized raffinose, containing six aldehydic functions, reacts with only three molecules of the reagent, and that the four aldehydic functions of the oxidized trehalose molecule react with only two. The reactions of periodate-oxidized carbo-... 

Anhydroderivate der Tagatose- bezw. Sorbose-phenyl-osazone und -phenylosotria-zole, by E. Schreier, G. Stohr, and E. Hardegger, Helv. Chim. Acta, 37 (1954) 35-41. 

N sulfuric acid produced D-lyxose as a sirup, characterized by its phenyl-osazone and by oxidation to D-lyxonic acid. 

Periodic acid oxidation t f non-glycosidic derivatives of the aldoses yields various products, the identity of which depends upon the nature of the substituent and its position in the molecule. 5,6-Dimethyl-glucoge,89 for example, gives dimethylglyceraldehyde. Glucose phenyl-osazone (XXIV)84 yields an unusual type of product, l-phenyl-4-benzeneazo-5-pyrazolone (XXVI), which apparently is derived by further oxidation of the expected three-carbon atom cleavage product (XXV). 

Treatment of truns-[PdCl2(PhCN)2] with biacetyl-bis(N-methyl, N-phenyl)osazone (L) in CH2C12 yields the square-planar osazone complex [PdCl2L], which under suitable conditions loses HC1 to yield the internally metallated complex (23), the structure of which has previously been determined.76,77 Studies of the condensation... 

The only recorded derivative of 3-methyl-L-rhamnose is the phenyl-osazone, which was prepared from 2,3-dimethyl-L-rhamnose.69... 

D-glucose phenylosazone anhydride from 3,6-anhydro-n-glucose phenyl-osazone (XVI) in the following manner. In support of this view it is... 

An instance of osazone formation in which substitution takes place on the second and third carbon atoms (in l-desoxy-n-psicose) has been reported. This case is of interest since the possibility arises that with other ketoses, as psicose, 2,3- as well as 1,2-osazones might be produced side by side. The commonest ketose, D-fructose, gives n-glucose phenyl-osazone with such extreme ease, that it is just possible the phenomenon may have escaped observation. 

Page 77, lines 7, 8, and 9 from bottom. Between 3,6-Anhydro-n-allose phenyl-osazone and "2-methyl- insert the heading 3,6-Anhydro-n-altrose. ... 

From L-allulose Steiger " prepared the phenylosazone (L-allose phenyl-osazone), which was hydrolyzed to L-allosone (LXIV) by means of benzaldehyde. The addition of hydrocyanic acid to the osone, followed by saponification with hydrochloric acid, then yielded crystalline l-alloascorbic acid (LXV), of m. p. 177° (decomp.) and - -29.3° in... 

The formazan reaction offers a means for clarifying the structure of the mixed A and mixed B osazones. The former was described by Voto6ek and Vondra6ek as acyclic n-glucose l-(iV -phenyl)-2-(Ar -methyl-A -phenyl)osazone, and the latter as acyclic n-glucose l-(A -methyl-i r -phenyl)-2-(V -phenyl)osazone. The Percivals assigned the same n-fruc-topyranose l-(Ar -phenyl)-2-(V -methyl-Ar -phenyl)osazone structure to the compounds, but differentiated them as probable syn and avli forms. 

Of these proposed structures, only that of the n-glucose l-(A -methyl-V -phenyl)-2-(A -phenyl)osazone, suggested by Voto6ek and Vondrafek for mixed osazone B, is theoretically unsuited for formazan formation since... 

However, since mixed osazone A undergoes no formazan reaction, even in alkaline solution, it would appear that the n-glucose l-(iV -methyl-iV -phenyl)-2-(iV -phenyl)osazone structure, - hitherto thought to be incapable of coupling, should be assigned to this substance (instead of to the mixed osazone B). This view is fully confirmed by recent work of Henseke and Hautschel. ... 

The formazan reaction, again, was found suitable for clarifying these points. Diels anhydro- D-glucose phenylosazone, like n-glucose phenyl-osazone, does not react in pyridine solution, while in an alkaline ethanol medium an osazone formazan is obtained which crystallizes as black nee-dles. Mild acetylation of this compound yields the black diacetate of Diels anhydro- D-glucose phenylosazone formazan. Analysis showed both acetyl groups to be oxygen-linked. 

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