ES270890A2 - 4-hydroxy (and acyloxy)-3-keto-steroids - Google Patents

Abstract

The invention comprises D 4,6-androstadiene-4,17b -diol-3-one and the corresponding 4,17-diacetate, 17a - methyl- D 4,6- androstadiene-4,11b ,17b - triol-3-one, 19-norD 4,6- androstadiene- 4,17b - diol-3-one, D 4,6- pregnadiene-4,17a -21-triol-3,11,20-trione and the corresponding 17a ,20:20,21-bismethylenedioxy and 17a ,20:20,21- bismethylenedioxy- 4-acetate compounds, D 4,6- pregnadiene- 4,11b ,17a ,21-tetrol- 3,20-dione and the corresponding 17a ,20:20,21- bismethylenedioxy compound, and D 4,6-pregnadiene-4,17a -diol-3,20-dione and the corresponding 20-ethylene ketal compound, and a process for the preparation of 4-hydroxy-3-keto-D 4,6-steroids by dissolving 3-keto-D 4-steroids in a tertiary aliphatic alcohol and then reacting with oxygen, e.g. atmospheric oxygen or pure oxygen, in the presence of an alkali metal salt of a tertiary aliphatic alcohol at a temperature of from 10 DEG to 50 DEG C. The above process may be extended in that 4-hydroxy-3-keto-D 4-steroids are prepared by hydrogenating the 4-hydroxy-3-keto-D 4,6-steroids until one mol of hydrogen is absorbed, and the resulting 4-hydroxy-3-keto-D 4-steroids may be further treated by acylating with a carboxylic acid chloride or anhydride to form 4-acyloxy-3-keto-D 4-steroids. In the above process the initial 3-keto-D 4-steroids may be of the androstane, 19-norandrostane, 17a - hydroxypregnane and 17a ,21- dihydroxypregnane series. It is preferable to pass the oxygen free from carbon dioxide and water into a solution of the steroid reactant or to allow a solution of the steroid in a large open container to stand in contact with the air. Therapeutic compositions comprise 4-hydroxy (or acyloxy)-3-keto-D 4- and D 4,6-steroids and a pharmacologically acceptable carrier. The compositions have hormonal properties as described in Specifications 839,908, 864,610, 876,721 and 888,665. Specification 899,219 also is referred to.