Verfahren zur Herstellung von Progesteron-Derivaten

1,214,380. 17α-(Amino and alkanoylamino)-progesterones. MERCK & CO. Inc. 27 Aug., 1968 [1 Sept., 1967], No. 40949/68. Heading C2U. Novel steroids of the formulµ (wherein R 1 is H or CH 3 ; R 3 is H or C 1-6 alkanoyl; and R 5 in Formula (III) is H, F or CH 3 and R 5 in Formula (XI) is H, CH 3 or, unless R 3 is alkanoyl, Cl) are prepared by the following processes Compound (I) (R 3 =alkanoyl) is heated with an alkali metal salt of a thiol R 7 SH (R7 is alkyl, cycloalkyl or optionally substituted phenyl or benzyl) in an inert atmosphere to give compound (II) (R 2 = SR 7 ; R 6 = H) which may be 3-acylated if desired, this is treated with Raney nickel in the presence of an unsaturated hydrocarbon to give (II) (R 2 = R 6 = H) which may be 3-acylated if desired, and this is oxidized to compound (III) (R 3 = alkanoyl) which is converted to the free 17α-amino compound (III) (R 3 = H) by a series of steps involving conversion to the 3-ketal compound (IV) (R 4 = oxo; R 8 = a cyclic ketal group), reduction to the 20-ol (IV) (R 4 = H(OH)), hydrolysis to the 17α- amino compound (IV) (R 3 = H; R 4 = H(OH)), oxidation to the 20-one (IV) (R 4 = oxo; R 3 = H) and acid hydrolysis; compound (IIIb) of its 6-methyl homologue is heated with chloranil to give compound (VI) or its 6-methyl homologue, compound (VI) is treated with monoperphthalic acid to give compound (IX) and this with HCl is glacial acetic acid gives compound (X); compound (IIIa) (R 3 = alkanoyl) is treated with an alkyl ester and a strong acid to give compound (VII) (R 6 = alkyl) and this with perchlory] fluoride gives compound (VIII) (R 3 = alkanoyl), after epimerization of any 6#-fluoro compound first formed, which can be converted to the free 17α-amino compound (VIII) (R 3 = H) via the 3-ketal and the 20-ol as detailed above. The use of 3-ethylene ketals is preferred. The novel steroids, which are stated to be aldosterone antagonists, to have anti-hormonal activity, and to be useful in the control and regulation of the female cycle, may be made up into pharmaceutical and veterinary compositions with suitable diluents, carriers, coatings and excipients. Pills, tablets, capsules, elixirs, syrups, boluses, drenches and injectable liquids are referred to.