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non-phosphorylative, may well effect the transfer of fructose into the cell.
Aqueous sodium metaperiodate oxidized the glycoside I11 with the consumption of 2.7 to 2.9 moles in 24 hours. From these oxidations, diDEPARTMENT OF BIOLOGICAL CHEMISTRY UNIVERSITY OF MICHIGAN MARSHALL W. NIRENBERG methylamine was isolated as the p-hydroxyazoANN ARBOR,MICHIGAN JAMES F. HOGG benzene p‘-sulfonic acid salt, formic acid as the RECEIVED OCTOBER 17, 1956 barium salt, glyoxal as the phenylosazone, formaldehyde as the dimedone derivative, and a small amount of acetaldehyde as the 2,4-dinitrophenylTHE STRUCTURE OF AMICETIN. A NEW hydrazone derivative. DIMETHYLAMINO SUGAR Glycoside I11 was hydrolyzed with the aid of a Sir : sulfonic acid resin (Dowex-SO), and from the Structure I, which incorporates the new di- hydrolysis the dirnethylamino sugar, aniosamine methylamino sugar amosamine (11), is presented for (11), was isolated as the crystalline hydrochloride, the antibiotic amicetin. In 1953, Flynn, Hinman, m.p. 192-193’ (calcd. for CsH1,N04.HC1: C, 42.30; Caron and Woolfl published evidence in support of H, 7.97; N, 6.15; C1, 15.57; mol. wt., 227.7. a partial structure for amicetin which included the Found: C, 42.09; H, 8.13; S , 6.13; C1, 15.18; a-methylserine, p-aminobenzoic acid, and cytosine mol. wt., 222), [cx]?~D 45.5 (lyoin water). 11remoieties of structure I with an unknown C14 frag- duced Fehling solution and consumed three moles of ment attached to the 1-position of cytosine. periodate fram which one equivalent of formaldehyde could be isolated as the dimeCHa CHI done derivative and two equivalents \ / of the volatile organic acid (formic) shown by titration. These data allow O ,:H , only a 2- or 4-deoxyaldohexose; the isolation of glyoxal from the C I oxi~ HOCH2,/‘.O)\o dation provides evidence for the 4-deoxy structure 11. The dirnethylamino group \was shown to be in the 3-position (p-dimethylaminoaldehyde) by application of the procedure of Hochstein and Regna,3 which compares the instability of various amino sugars in alkali; under the conditions they describe 11 lost 43y0 of one equivalent of dirnethylamine in two hours. The structure of the neutral moiety I V was deduced from the following data. The stable hemiketal structure for 111 demands a pyranose or furanose rine: the fact that the two CCHI methyl gFoups must reside in IV indicates the furanose form of I V in the CH 3/\o’
