The esterification of prednisolone (I) with ethyl orthocarbonate (II) by means of p-toluenesulfonic acid in dioxane gives prednisolone 17,21-(diethylorthocarbonate) (III), which is carefully hydrolyzed with acetic acid water yielding cyclic prednisolone 17-(ethyl carbonate) (IV). Finally, this compound is esterified with propionyl chloride or propionyl anhydride in pyridine or CH2Cl2-dimethylaminopyridine, respectively.