SYNTHESIS OF C-21 GLUCOSIDURONATES OF CORTISONE AND RELATED CORTICOSTEROIDS

On treatment with methyl 2,3,4-tri-O-acetyl-1-bromo-1-deoxy-α-D-glucuronate, cortisone yielded the corresponding 21-glucosiduronate triacetate methyl ester. Removal of the acetyl groups from the conjugate by transesterification with sodium hydroxide in methanol produced the corresponding methyl glucosiduronate. Hydrolysis of the methyl ester linkage with sodium hydroxide followed by acidification produced cortisone-21-glucosiduronic acid. The methyl triacetyl ester of cortisone-21-glucosiduronic acid formed a 3,20-bissemicarbazone which was reconverted into the 3,20-dioxo derivative by treatment with pyruvic acid. Analogous glucosiduronate derivatives have been synthesized from cortisol, 11-deoxycortisol, corticosterone, 11-dehydrocorticosterone, and 11-deoxycorticosterone. Steroidal glucosiduronic acids can be separated from inorganic salts and acids by adsorption on a polystyrene resin (Amberlite XAD-2) which does not adsorb the inorganic components; the glucosiduronic acids can be eluted from the resin by use of ethanol. © 1969, American Chemical Society. All rights reserved.