TY - JOUR
T1 - Kinetics and mechanism of oxidation of erythro-series pentoses and hexoses by N-chloro-p-toluenesulfonamide
AU - Rangappa, Kanchugarakoppal S.
AU - Raghavendra, Manikanahally P.
AU - Mahadevappa, Dandinasivara S.
AU - Gowda, D. Channe
N1 - Funding Information:
We thank Professor Derek Horton, The American University, Washington, DC, for suggestions regarding the mechanism, Dr. Roberta Merkle, Complex Carbohydrate Research Center, University of Georgia, and Dr. Lewis Pannell, NIDDK, NIH, for GLC–MS analyses. M.P.R. is grateful to the University of Mysore for the University Grants Commission (UGC), India, research fellowship. D.S.M. thanks the UGC, India, for awarding the emeritus Professorship.
PY - 1998/1
Y1 - 1998/1
N2 - The kinetics and mechanism of oxidation of D-glucose, D-mannose, D- fructose, D-arabinose, and D-ribose with chloramine-T in alkaline medium were studied. The rate law, rate = k [Chloramine-T] [Sugar] [HO-]2, was observed. The rate of the reaction was influenced by a change in ionic strength of the medium, and the dielectric effect was found to be negative. The latter enabled the computation of d(AB), the size of the activated complex. The reaction rate was almost doubled in deuterium oxide. Activation energies were calculated from the Arrhenius plots. HPLC and GLC-MS analyses of the products indicated that the sugars were oxidized to a mixture of aldonic acids, consisting of arabinonic, ribonic, erythronic, and glyceric acids. Based on these data, a plausible mechanism involving the aldo-enolic anions of pentoses and keto-enolic anions of hexoses is suggested.
AB - The kinetics and mechanism of oxidation of D-glucose, D-mannose, D- fructose, D-arabinose, and D-ribose with chloramine-T in alkaline medium were studied. The rate law, rate = k [Chloramine-T] [Sugar] [HO-]2, was observed. The rate of the reaction was influenced by a change in ionic strength of the medium, and the dielectric effect was found to be negative. The latter enabled the computation of d(AB), the size of the activated complex. The reaction rate was almost doubled in deuterium oxide. Activation energies were calculated from the Arrhenius plots. HPLC and GLC-MS analyses of the products indicated that the sugars were oxidized to a mixture of aldonic acids, consisting of arabinonic, ribonic, erythronic, and glyceric acids. Based on these data, a plausible mechanism involving the aldo-enolic anions of pentoses and keto-enolic anions of hexoses is suggested.
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U2 - 10.1016/S0008-6215(97)00243-7
DO - 10.1016/S0008-6215(97)00243-7
M3 - Article
C2 - 9691439
AN - SCOPUS:0031775606
SN - 0008-6215
VL - 306
SP - 57
EP - 67
JO - Carbohydrate Research
JF - Carbohydrate Research
IS - 1-2
ER -