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Nitrosation of Sugar Oximes: Preparation of 2‐Glycosyl‐1‐hydroxydiazene‐2‐oxides
Author(s) -
Brand Jörg,
Huhn Thomas,
Groth Ulrich,
Jochims Johannes C.
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500325
Subject(s) - nitrosation , chemistry , oxime , fructose , xylose , aqueous solution , organic chemistry , lactose , sugar , oxide , medicinal chemistry , nuclear chemistry , fermentation
Oximes of glucose, xylose, lactose, fructose, and mannose have been prepared. Nitrosation of the oximes of glucose, xylose, and lactose with NaNO 2 /HCl afforded 2‐(β‐glycopyranosyl)‐1‐hydroxydiazene‐2‐oxides, which were isolated as salts 13 , 22 , and 28 . Nitrosation of fructose oxime 29 furnished fructose, whereas nitrosation of mannose oxime 30 with NaNO 2 /HCl afforded the 1‐hydroxy‐2‐(β ‐d‐ mannopyranosyl)diazene‐2‐oxide 32 , from which the p ‐anisidinium salt 31 and the sodium salt 33 were prepared. However, nitrosation of 30 with isopentyl nitrite in aqueous solutions of CsOH or KOH resulted in the formation of the 2‐(α‐ D ‐mannofuranosyl)‐1‐hydroxydiazene‐2‐oxide salts 34 and 35 , respectively. Methylation of the ammonium 2‐(β‐ D ‐glucopyranosyl)‐1‐hydroxydiazene‐2‐oxide 13 yielded the 1‐methoxy compound, which was benzoylated to afford the tetra‐ O ‐benzoate 14 a , the structure of which was confirmed by X‐ray diffraction analysis. From the glucose O ‐methyloximes 15 and 16 the N ‐methoxy‐ N ‐nitroso‐2,3,4,6‐tetra‐ O ‐acetyl‐β‐ D ‐glucopyranosylamine 18 was prepared. The structure of this compound was confirmed by X‐ray diffraction analysis. Treatment of acetobromoglucose with cupferron furnished the 1‐(2,3,4,6‐tetra‐ O ‐acetyl‐β‐ D ‐glucopyranosyloxy)‐2‐phenyldiazene‐2‐oxide 20 .