Photochemical transformations. Part XXIV. The synthesis of 18-hydroxyoestrone

Abstract

Oxidation of 17β-carbamoyloestra-1,3,5(10)-trien-3-ol methanesulphonate with lead tetra-acetate and iodine under illumination gave, on treatment with aqueous sodium hydrogen sulphite and further processing, the corresponding 18,20-anhydride. Working up with aqueous caustic alkali in dioxan afforded the 18,20-dicarboxylic acid, conveniently characterised as the dimethyl ester. By a series of more conventional reactions the anhydride, or the corresponding dimethyl ester, were transformed into 18-hydroxyoestrone diacetate and thence into 18-hydroxyoestrone.

A smooth photochemical fragmentation reaction of a tertiary diphenylcarbinol nitrite has been noted.