Hydrolysis of glycosylamines

The pH (or Ho - see Chapter 3, footnote xi) dependences of the rates of hydrolysis of glycosylamines are bell-shaped, with the maximimum at a pH... 

Figure 1.24 Mutarotation and hydrolysis of glycosylamines, illustrated with N-aryl glucosylamines.

The ease of hydrolysis of glycosylamines parallels the base strength of the corresponding amine, with the exception of glucosylamine itself 12, 62). Normal acetic acid was found to be a more effective hydrolyzing agent than 0.5 N hydrochloric acid, whereas the effect of dilute sodium hydroxide... 

The imonium ion intermediate (III) is used by Isbell and Frush (9a) to account for the limitation of the hydrolysis of glycosylamines to a narrowly restricted pH range. 

Substances of structures (105) and (106) may be intermediates in the Amadori rearrangement of glycosylamines (104) when this reaction is catalyzed by certain /3-dicarbonyl compounds. Hydrolysis of (106) would give the products of the rearrangement, the V-substituted 1-aniino-l-deoxy-D-fructoses (109). Hodgehas obtained some evidence for the existence of intermediate compounds in the Amadori rearrangement he formulated these as the branched-chain amino ketoses (78, X = iV-alkyl or V-aryl). 

Isbel HS, Frush HL (1958) Mutarotation, hydrolysis and rearrangement reactions of glycosylamines. J Org Chem 23 1309-1319... 

When D-glucuronic acid was treated with aniline and a water-soluble carbodiimide, the glucuronamide-glycosylamine (47) was formed in high yield. Hydrolysis of the glycosylamine occurred readily to give N-phenyl-D-... 

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