Halogenated steroids

Process for the manufacture of halogenated steroids of the formula ##STR5## in which X represents a halogen atom having a maximum atomic number of 17,

• Y represents a hydrogen atom or hydroxyl, and
• R represents an alkyl radical having a maximum of 6 carbon atoms,
• the dotted line in the 1,2-position representing the additional double bond of a 1,2-dehydro derivative, wherein:
• (a) 21-(fluoro or chloro)-3.beta.-hydroxy-16-methyl-pregna-5,16-dien-20-one 3-lower alkanoyl ester is treated with a peracid and to form the corresponding 5,6-epimers, which are separated from each other in a resulting mixture of 5,6;16.alpha.,17-diepoxides, is treated with hydrogen fluoride, or any obtained 5.beta.,6;16.alpha.,17-diepoxide is reacted with a strong oxygen-containing acid, to form the resulting 5.alpha.,6.beta.,17.alpha.-trihydroxy-16-methylene compound which is then treated with an organic sulphonyl halide in the presence of 2,4,6-collidine or 2,6-lutidine, to form the resulting 5.alpha.,6-epoxy-17-.alpha.-hydroxy-16-methylene compound, which is then reacted with hydrogen fluoride, to form the corresponding 21-(fluoro or chloro) 6.beta.-fluoro-5.alpha.,17.alpha.-dihydroxy-3.beta.-lower alkanoyloxy-16-methylene-pregnan-20-one,
• (c) the resulting 21-(fluoro or chloro)-6.beta.-fluoro-5.alpha.,17.alpha.-dihydroxy-3.beta.lower alkanoyloxy-16-methylene-pregnan-20-one, the two free hydroxyl groups are esterified by a lower alkanecarboxylic acid,
• (d) the resulting 21-(fluoro or chloro)-6.beta.-fluoro-3.beta.,5.alpha.,17.alpha.-trihydroxy-16-methylene- pregnan-20-one 3-lower alkanoyl-5,17-di-lower alkanecarbonyl ester is catalytically hydrogenated,
• (e) the resulting 21-(fluoro or chloro)-6.beta.-fluoro-3.beta.,5.alpha.,-17.alpha.-trihydroxy-16.beta.-met hyl-pregnan-20-one 3-lower alkanoyl-5,17-di-lower alkanecarbonyl ester, the esterified 3-hydroxyl group is freed by selective hydrolysis and subsequently oxidised into the 3-oxo group,
• (f) the resulting 21-(fluoro or chloro)-6.beta.-fluoro-5.alpha.,17.alpha.-di-lower alkanecarbonyloxy-16.beta.-methyl-pregnane-3,20-dione is treated with an acid in order to remove the 5-positioned lower alkanecarbonyloxy group and, with or without converting any resulting compound having 6.beta.-fluoro, by catalytic treatment with a strong acid, into the 6.alpha.-fluoro isomer, and, where Y represents hydroxyl, the resulting end product of the formula A in which Y represents hydrogen is hydroxylated in the 11.beta.-position by means of the enzymatic system of a 11.beta.-hydroxylating micro-organism, and where the compound of formula A is a 1,2-dehydro compound the resulting 1,2-saturated end product of the formula A is dehydrogenated.