ABSTRACT
N-(m-Nitrophenyl)-beta-D-glucopyranosylamine (Gln), N-(N-methylphenyl)-beta-D-glucopyranosylamine (Glm), N-beta-D-glucopyranosylpyrazole (Glp), and N-beta-D-glucopyranosylimidazole (Gli) have been synthesized. Their basicity constants, pKb, determined in methanol were, respectively, 14.99, 14.36, 15.04, and 9.74. The derivatives of secondary amines (Glm, Glp, and Gli) did not mutarotate in methanol in the presence of 3,5-dinitrobenzoic acid and hydrochloric acid. The heats of formation and entropies were calculated by the AM1 and PM3 methods for the glucosylamines and their cations under consideration of two plausible protonation centers. Thermodynamic parameters for the proton transfer in the reaction: glucosylamine + CH3OH2+ = glucosylamineH+ + CH3OH were determined and the protonation center in the glucosylamine molecule was identified. The mechanism of mutarotation of the glucosylamines is discussed and the conclusion made that formation of an acyclic immonium cation is not a satisfactory condition for the reaction to proceed.
Subject(s)
Glucosamine/analogs & derivatives , Glucosamine/chemistry , Methanol/chemistry , Protons , Carbohydrate Conformation , Glucosamine/chemical synthesis , Molecular StructureABSTRACT
Rate constants for the mutarotation reaction of N-(p-chlorophenyl)-beta-D-glucopyranosylamine (NGlc) in methanol have been determined in the presence of transition metal chlorides (MCl(2)), at 25 degrees C. The activity of the metal ions catalyzing the alpha-pyranoside<-->beta-pyranoside interconversion has been found to increase in the following series: Mn(2+)Subject(s)
Glucosamine/analogs & derivatives
, Glucosamine/chemistry
, Metals/chemistry
, Methanol/chemistry
, Carbohydrate Conformation
, Catalysis
, Kinetics
, Molecular Structure
ABSTRACT
Four isomers of methyl 2-deoxy-D-arabino-hexosides were isolated by HPLC as chromatographically homogeneous compounds. The rates of pyranoside isomerization (alpha(p) and beta(p)) at 40 degrees C and of furanoside isomerization (alpha(f) and beta(f)) at 26 degrees C were determined. A mechanism has been suggested for transformations taking place during isomerization of methyl 2-deoxy-D-arabino-hexosides in methanolic solution catalyzed with hydrogen chloride.
