Process for the preparation of 17.alpha.-hydroxyprogesterones and corticoids from androstenes

A process for the preparation of a steroid of the formula ##STR19## where R.sub.3 is an oxygen atom (O) or a hydroxyl group (HO) with the proviso that when R.sub.3 is (O) there are double bonds between C.sub.3 and R.sub.3 and between C.sub.4 and C.sub.5, and when R.sub.3 is (HO) there is a single bond between C.sub.3 and R.sub.3 with a double bond between C.sub.5 and C.sub.6 ;

• where R.sub.6 is a hydrogen or fluorine atom or methyl group;
• where R.sub.9 is a hydrogen, fluorine, chlorine, or bromine atom, or hydroxyl group;
• where R.sub.11 is (H), (H,H), (H,.alpha.OH), (H,.beta.OH) or (O);
• where R.sub.16 is a hydrogen atom or methyl group;
• where .about. indicates the attachment of the R.sub.16 group in the alpha or beta configuration;
• and where is a single or double bond which comprises starting with a steroidal propargyl alcohol of the formula ##STR20## where R.sub.3, R.sub.6, R.sub.9, R.sub.11, R.sub.16, .about., and are defined above and subjecting the steroidal propargyl alcohol IV to the following reactions:
• 1. sulfenylating with a substituted sulfenylating agent of the formula R.sub.17 -S-M;
• where M is a chlorine or bromine atom, phenylsulfone, phthalimide or imidazole group;
• where R.sub.17 is alkyl of one thru 10 carbon atoms, trichloromethyl, phenyl or phenyl substituted with one thru 3 nitro groups or substituted with one thru 3 trifluoromethyl groups, aralkyl of 7 thru 12 carbon atoms, phthalimide, (R.sub.121).sub.2 -N where R.sub.121 is alkyl of one thru 10 carbon atoms, phenyl, phenyl substituted with alkyl of one thru 4 carbon atoms, aralkyl of 7 thru 12 carbon atoms with the proviso that the two R.sub.121 groups may be the same or different, to form an allene sulfoxide of the formula ##STR21## where R.sub.3, R.sub.6, R.sub.9, R.sub.11, R.sub.16, R.sub.17, .about., and are defined above;
• 2.