MIGRATION OF METHYLTHIO GROUP IN SOLVOLYSIS OF SOME METHYL 1-THIO-6-O-TOLUENE-P-SULPHONYL-BETA-D-GLYCOPYRANOSIDES

The hydrolysis and methanolysis of methyl 1-thio-6-O-toluene-p-sulphonyl-β-D-glucopyranoside proceeds with migration of the methylthio group to C-6. Acetolysis of methyl 1-thio-6-O-toluene-p-sulphonyl-β-D-glucopyranoside triacetate and of the corresponding galactoside likewise gives 6-S-methyl-6-thio compounds. The stereo-chemical outcome at C-1 of these reactions is discussed. Replacement of the methylthio group of the methyl 1-thio-6-O-toluene-p-sulphonyl-α- and -β-D-glucopyranosides by an acetoxyl group, using mercuric acetate in acetic acid, proceeds mainly with inversion of configuration at C-1. © 1968.