GB1269234A - 09-alkyl steroids and a process for the preparation thereof - Google Patents

Abstract

1,269,234. 19-Alkylsteroids. F. HOFFMANLA ROCHE & CO. A.G. 13 May, 1969 [15 May, 1968], No. 24320/69. Heading C2U. The invention comprises compounds of Formulµ I and II wherein R 1 is H or C 1-6 alkyl; R 2 is free, esterified or etherified hydroxy; R 3 is H, C 1-6 alkyl, C 2-6 alkenyl or C 2-6 alkynyl; R is a 3 - oxo - #<SP>4,6</SP>/#<SP>1,4,6</SP>, 3 - hydroxy - #<SP>4,6</SP>, 3-acyloxy - #<SP>4</SP>/#<SP>4,6</SP>/#<SP>3,5</SP>/#<SP>2,4,6</SP> or 3 - alkoxy - #<SP>4</SP>/#<SP>4,6</SP>/ #<SP>3,5</SP>/#<SP>3,5,7</SP> system; and R<SP>5</SP> is alkoxy. Preparation of compounds I wherein R is a 3-alkoxy-#<SP>3,5</SP> group is by reduction, alkylation, alkenylation or alkynylation of the 17-oxo group of compounds II. Subsequent dehydrogenation gives 3-oxo-#<SP>4,6</SP> compounds which can also be obtained by dehydrogenation of the corresponding 3-oxo-#<SP>4</SP> compounds as can also the 3-oxo-#<SP>1,4,6</SP> compounds. Enol esterification/etherification then yields 3-alkoxy-#<SP>3.5</SP>/ #<SP>3,5,7</SP> and 3 - acyloxy - #<SP>3,5</SP>/#<SP>2,4,6</SP> compounds. The 3 - alkoxy/acyloxy - #<SP>4</SP>/#<SP>4,6</SP> compounds are obtained conventionally from the corresponding 3-ols. The 17-hydroxy group can also be esterified and etherified. A 3-oxo-#<SP>4,6</SP> group may be reduced to a 3-hydroxy-#<SP>4,6</SP> group. Preparation of compounds II is by enol etherification of the corresponding 4-en-3-ones. 17α - Ethynyl - 19 - ethylandrost - 4 - ene- 3#,17#-diol and -3α,17#-diol are prepared by NaBH 4 reduction of the corresponding 3-one. Compounds I are said to influence gonadotropin economy and to inhibit the action of progesterone, and may be made up with carriers into pharmaceutical compositions for oral, parenteral and rectal administration.