Selective oxidation of primary alcohol groups of beta-cyclodextrin mediated by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)

beta-Cyclodextrin (beta-CD) was reacted with catalytic amounts of 2,2,6,6-t etramethylpiperidine-1-oxyl radical (TEMPO), sodium hypochlorite and sodium bromide at 2 degrees C and a pH value of 10 in water. The primary alcohol groups were selectively oxidized into carboxylate groups within a few minut es, and mono- and dicarboxy-beta-cyclodextrin sodium salts were isolated an d characterized by H-1, C-13 NMR and mass spectroscopy. With this reaction system, the degradation of the cyclodextrin was limited, provided the oxida tion was performed at 2 degrees C, at constant pH value of 10, with catalyt ic amounts of TEMPO and controlled quantities of sodium hypochlorite and so dium bromide for the continuous regeneration of the oxoammonium salt. (C) 2 000 Elsevier Science Ltd. All rights reserved.