GB628258A - Manufacture of intermediates in the synthesis of adrenal cortical hormone - Google Patents

Abstract

D 17,26 - 3 : 11 - Diketo - 21 - acyloxypregnenes are manufactured by the action of strong oxidizing agents on D 17,20-3-hydroxy-11-keto-21-acyloxypregnenes having an oxidation-resistant acyloxy substituent (obtainable by esterifying D 17,20 - 3 : 21 - dihydroxy - 11-ketopregnene with an aliphatic or aromatic monobasic or preferably dibasic acid or anhydride such as succinic, phthalic or benzoic acid or succinic, acetic or phthalic anhydride). The oxidation is preferably effected in dilute solution at about 15 DEG C. using a slight excess of the oxidizing agent over the stoichiometric amount required to oxidize the 3-hydroxy group. The product may be saponified to the 21-hydroxy compound, which may then be reacylated in order to introduce any desired acyl group. In an example, D 17,20-3(a )-hydroxy - 11 - keto - 21 - hemisuccinoxypregnene is treated with chromic acid in glacial acetic acid to produce D 17,20-3 : 11-diketo-21-hemisuccinoxypregnene, which is saponified with aqueous potassium carbonate and the product re-esterified by treatment with acetic anhydride and pyridine. The starting material may be replaced by the corresponding compound in which the 3-hydroxy group has the cis configuration. Additional oxidizing agents specified are chromium trioxide, a chromate salt in an acid medium, and aluminium phenoxide in acetone. The Specification as open to inspection under Sect. 91 comprises also the use as starting materials of esters (e.g. the acetic, propionic, butyric, valeric, caproic capric, benzoic, toluic or phenylacetic esters) of D 17-20-3-hydroxy-11 keto - 21 - acyloxypregnenes. This subject-matter does not appear in the Specification as accepted.