17α-Chloro-17β-hydrocarbonsulfinyl-1,4-androstadienes and the corresponding 17β-hydrocarbonsulfonyl derivatives and their use as anti-acne agents

Claim 2

A steroid having the formula: ##STR7## wherein R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms; X is hydrogen or fluorine; Y is oxygen, or hydrogen when X is hydrogen, and n is 1 or 2.

Claim 3

A compound of claim 1 having the formula: ##STR8## wherein X is fluorine or hydrogen, Z and Z' are hydrogen, methyl or chlorine.

Claim 4

A compound of claim 1 having the formula: ##STR9## wherein X is fluorine or hydrogen, Z and Z' are hydrogen, methyl or chlorine.

Claim 5

A compound of claim 3 which is 17α-chloro-17β-[R]-benzylsulfinyl-1,4-androstadiene-3,11-dione.

Claim 6

A compound of claim 3 which is 17α-chloro-17β-(4'-chlorobenzylsulfinyl)-1,4-androstadiene-3,11-dione.

Claim 7

A compound of claim 3 which is 17α-chloro-17β-(2',4'-dichlorobenzylsulfinyl)-1,4-androstadiene-3,11-dione.

Claim 8

A compound of claim 3 which is 17α-chloro-17β-(3',4'-dichlorobenzylsulfinyl)-1,4-androstadiene-3,11-dione.

Claim 9

A compound of claim 3 which is 17α-chloro-17β-(2'-methylbenzylsulfinyl)-1,4-androstadiene-3,11-dione.

Claim 10

A compound of claim 3 which is 9α-fluoro-17α-chloro-17β-[R]-benzylsulfinyl-1,4-androstadiene-3,11-dione.

Claim 11

A steroid having the formula: ##STR10## wherein A is hydrogen, α-fluoro, α-bromo; B is hydroxyl; or together A and B form a 9β,11β-epoxy group or a 9(11) bond; and R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms.

Claim 12

A steroid having the formula: ##STR10## wherein A is hydrogen, α-fluoro, α-bromo; B is hydroxyl; or together A and B form a 9β,11β-epoxy group or a 9(11) bond; and R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms.

Claim 13

The process for preparing a 3-oxo-1,4-androstadiene having a substituent at C-17 of the following partial formula: ##STR11## wherein R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms; which comprises reacting a 3-oxo-1,4-androstadiene having a substituent at C-17 of the following partial formula: ##STR12## wherein R has the same meaning as above, with excess equivalents of a chlorine source in a mixture of water and a water soluble base, in the temperature range of from about -78° C. to about 25° C.

Claim 14

The process for preparing a 3-oxo-1,4-androstadiene having a substituent at C-17 of the following partial formula: ##STR11## wherein R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms; which comprises reacting a 3-oxo-1,4-androstadiene having a substituent at C-17 of the following partial formula: ##STR12## wherein R has the same meaning as above, with excess equivalents of a chlorine source in a mixture of water and a water soluble base, in the temperature range of from about -78° C. to about 25° C.

Claim 15

The process of claim 11 wherein said 3-oxo-1,4-androstadiene starting compound is a 9-unsubstituted-3,11-dioxo-1,4-androstadiene having a substituent at C-17 as defined in claim 11.

Claim 16

The process of claim 11 wherein said chlorine source is chlorine gas, iodobenzenedichloride, N-chlorosuccinimide or 1-chlorobenzotriazole.

Claim 17

The process of claim 11 wherein said water soluble base is a nitrogenous base selected from the group consisting of pyridine, trialkylamine or collidine.

Claim 18

The process of claim 11 wherein said temperature range is preferably about 0° C. to -40° C.

Claim 19

The process of claim 11 wherein said excess equivalents of chlorine source are in the range of from about 2-5 and wherein there are at least two equivalents of said water soluble base.

Claim 22

A pharmaceutical composition for the treatment of acne comprising an anti-acne effective amount of a steroid having the formula: ##STR14## wherein R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms; X is hydrogen or fluorine, Y is oxygen or hydrogen when X is hydrogen, and n is 1 or 2; together with a non-toxic, pharmaceutically acceptable carrier.

Claim 23

A pharmaceutical composition for the treatment of acne comprising an anti-acne effective amount of a steroid having the formula: ##STR14## wherein R is benzyl, phenethyl, methylbenzyl, dimethylbenzyl, chlorobenzyl, dichlorobenzyl and an alkyl group having up to 8 carbon atoms; X is hydrogen or fluorine, Y is oxygen or hydrogen when X is hydrogen, and n is 1 or 2; together with a non-toxic, pharmaceutically acceptable carrier.