Process for the preparation of 21-halogeno-21-desoxy-17α-acyloxy-20-keto-pregnenes

Claim 2

The process for the preparation of a 21-halogeno-17α-acyloxy-20-ketopregnene, said halogeno being chloro or bromo, which comprises the reaction of a 17,21-dihydroxy-20-ketopregnene 17,21-orthoester with a halide reagent selected from the group consisting of triphenylsilyl halide, tri-(alkyl substituted phenyl)-silyl halide, and tri-lower alkylsilyl halide, said halide being chloride or bromide, in an organic solvent.

Claim 3

A process in accordance with claim 1 wherein the organic solvent is a halogenated hydrocarbon, and said process is carried out at the relux temperature of said solvent.

Claim 4

The process of claim 1 wherein said halide reagent is trimethylsilyl halide.

Claim 5

The process of claim 1 wherein said 17,21-dihydroxy-20-ketopregnene 17,21-orthoester is a member selected from the group consisting of a compound defined by formula I: ##SPC3## wherein Y is hydrogen, oxo, hydroxy, lower alkanoyloxy, chlorine or fluorine; Z is hydrogen, fluorine, chlorine or bromine when Y is oxo, hydroxy or lower alkanoyloxy; Z is chlorine or bromine when Y is chlorine or fluorine; and Z is hydrogen when Y is hydrogen R 1 is alkyl of 1 to 8 carbon atoms, or phenyl; R 2 is hydrogen, α -methyl, β-methyl, α-acyloxy of the formula ##STR3## wherein R 3 is a lower alkyl having 1 to 8 carbon atoms; R 4 is alkyl having 1 to 4 carbon atoms; and the 1-dehydro-, 6-dehydro- and 1,6-bis-dehydro analogs of the compounds of formula I.

Claim 6

The process of claim 4 wherein the 17α ,21-dihydroxy-20-ketopregnene 17,21-orthoester is a compound of the formula: ##SPC4##

Claim 7

A process for preparing a 21-chloro-17-acyloxy-20-ketopregnene from a 17,21-dihydroxy-20-ketopregnene 17,21-orthoester which comprises reacting a 17,21-dihydroxy-20-ketopregnene 17,21-orthoester with trimethylsilyl chloride in a halogenated hydrocarbon solvent at the reflux temperature of said solvent.

Claim 8

A process for preparing a 21-chloro-17-acyloxy-20-ketopregnene from a 17,21-dihydroxy-20-ketopregnene 17,21-orthoester which comprises reacting a 17,21-dihydroxy-20-ketopregnene 17,21-orthoester with trimethylsilyl chloride in a halogenated hydrocarbon solvent at the reflux temperature of said solvent.

Claim 9

The process of claim 6 wherein the 17,21-dihydroxy-20-ketopregnene 17,21-orthoester has the formula: ##SPC5## wherein Y is hydroxy or chlorine; Z is hydrogen, fluorine, chlorine, or bromine when Y is hydroxy, and Z is chlorine when y is chlorine; R 1 is alkyl of 1 to 8 carbon atoms, or phenyl; R 2 is hydrogen, α -methyl, β-methyl, α-acyloxy of the formula ##STR4## wherein R 3 is a lower alkyl having 1 to 8 carbon atoms; and R 4 is alkyl of 1 to 4 carbon atoms.