ES255441A1 - Procedure for the preparation of 16-methylene-steroids (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

Process for the preparation of 16-methylene steroids of the formula A ** (See formula) ** Z = H o well OR1 R1 = H or acyl X = H o well F and its 1-dehydro derivatives, characterized in that it is treated with an epoxidizing agent 16-methyl-5,16-pregnadien-3 beta-ol-20-one or its 3-acylate and in the 16alpha, 17alpha- oxide-steroid II thus prepared, in the order of succession that is desired, a) the 16beta-methyl-16alpha, 17alpha-oxide group is dissociated by treatment with acid, with formation of a 16-methylene group and a 17alpha-OH group, b) the 3beta-OR1-5-ene system is transformed by standard methods into the 3-keto-4-ene system, c) a hydroxyl group is introduced in position 11, by incubation with hydroxylating microorganisms, d) In order to prepare the corresponding steroids with an oxygen function in position 21, the substituent Z = H is replaced by consecutive treatment with elemental bromine or alkaline solution of iodine and alkaline acylate, by the radical Z = O-acyl, and e) In order to prepare the corresponding 1-dehydro-derivatives, the saturated 1,2-bond is transformed, by treatment with ordinary dehydration agents, chemical or microbiological, in a double bond 1,2 with formation of a compound of formula B ** (See formula) ** in which X and R1 have the meaning indicated above and another double bond may exist in position 1,2, and by the fact that, when a 16-methylene steroid of the formula A in which X = F is to be prepared, a fluorine atom in the 9alpha position is introduced into the compound B by standard methods, with formation of a compound of formula C ** (See formula) ** in which Z has the meaning indicated above and another double bond may exist in position 1,2. (Machine-translation by Google Translate, not legally binding)