CHEMICAL STUDIES WITH 11-OXYGENATED STEROIDS. IV^1,2 THE REACTION OF HYPOHALOUS ACIDS WITH STEROID ENOL ACETATES

Abstract

Bedoukian has reported the synthesis of several -bromoketones by the addition of bromine to the enol acetates of the parent ketones (1). This method was used in the steroid field by Fieser and Huang-Minlon to introduce a 17bromine atom in the synthesis of 3-acetoxy-5,6,17-tribromopregnan-20-one from 3-acetoxy-5-pregnen-20-one (2). Similarly, by treating the 20 enol acetate of 3-acetoxy-5-pregnen-20-one with bromine, Moffett and Weisblat introduced bromine at C-21, obtaining 3-acetoxy-5,6,21-tribromopregnan-20-one (3).Reich and Lardón added hypobromous acid (N-bromacetamide in aqueous acid solution) to the enol acetates of cholestenone and methyl 3-keto-4-etiocholenate and obtained the respective 6-bromo-A4-3-ketones (4). This reaction involves 1,4 addition to the conjugated diene system of the enol acetates. Djerassi and Lenk treated a number of enol acetates with N-iodosuccinimide

Synthesis of ring-Aand -Bsubstituted 17α-acetoxypregnan-20-one derivatives with potential activity on the digitalis receptor in cardiac muscle

“…168-173 "C). 3p, 17x-Diacetoxy-5cx-hydroxypregnune-6,20-dione (14).-To a solution of 3p, 17a-diacetoxypregn-5-en-20-one (1 b) (2.1 g) in a mixture of dioxane (50 ml) and water (14 ml) was added Nbromosuccinimide (4.46 g, 5 equiv.). The mixture was stirred at room temperature for 22 h and then diluted with water and extracted with ether.…”