The nucleophilic replacement reactions of tetra-O-acetyl-α-D-glucopyranosyl bromide (3) with sodium azide and potassium thiolacetate has led to the formation of 2,3,4,6-tetra-O-acetyl-ß-D-glucopy- ranosyl azide (4) and 2,3,4,6-tetra-0-acetyl-1-S- acetyl-1-thio-ß-D-glucopyranose (10) in quantitative yields. The compound (4) was selectively reduced to yield corresponding amine (5) which was blocked by acid anhydride. Zemplen's method of deacylation yield (7 and 9) as crystalline derivatives. Tetra-0-acetyl-ß-D-glucopyranosylsulfenyl bromide (11), an unstable crystalline compound was obtained by shaking 2,3,4,6- tetra -0- acetyl-1-S-acety1-1-thio-ß-D-glucopyranose with excess of bromine in carbon tetrachloride at low temperature. The electrophilic behavior of sulfur atom in compound (11) has been studied.