GB1128044A - 13-(c) alkyl-11-oxygenated gonenes - Google Patents

Abstract

1,128,044. 13 - (C 2-5 alkyl) - 11 - oxygenated gonenes. H. SMITH. 6 Oct., 1965 [6 Oct., 1964], No.42356/65. Heading C2U. Novel steroids of the structure (wherein R<SP>1</SP> is C 2-5 alkyl; X is CO or a ketal thereof, CH(OH) or CH(O acyl); Z is O or H(OH) or ketals, ethers or esters thereof; W is H or OH or O acyl; R is H or one or more C 1-6 alkyl groups at one or both of the 6- and 7- positions; and Y is OH or an ester or ether thereof when ring A is aromatic, or is etherified OH when ring A has the #<SP>2</SP> <SP>5(10)</SP>-diene system, or is =O, H(OH) or H(O acyl) when ring A has a #<SP>4</SP> or 5(10) double bond; and there is an optional #<SP>9(11)</SP> double bond present when Z is acyloxy) and the novel D-homo analogues thereof, are prepared from the corresponding 11 - unsubstituted - 16 - unsubstituted -#<SP>1</SP>'<SP>3</SP>'<SP>5(10)</SP>- 3-hydroxy or esterified or etherified hydroxy steroids which may also contain a #<SP>16</SP> double bond by hydroboration, i.e. reaction with a boron hydride and subsequent oxidation to introduce a hydroxy group or groups into the steroid nucleus, followed, if desired, by (1) Birch reduction to a 2,5(10)-diene; (2) hydrolysis of the Birch reduction product to give a #<SP>4</SP>- or #<SP>5(10)</SP>-3-keto compound; (3) oxidation of an 11-, 16- or 17-OH group to a corresponding keto group; (4) reduction of an 11-keto group to an 11#-hydroxy group or 11-ketalization; and (5) esterification of free OH groups. Other processes may also be effected on the products, e.g. reduction of a 17-one to a 17-ol, and enol acylation of an 11-one to a #<SP>9(11)</SP>-11-acyloxy compound. The hydroboration process results in a ring C saturated 11α-hydroxy compound which, if the starting material contains a #<SP>16</SP> double bond, contains a 16α-hydroxy group with ring D saturated. The structure (I) above includes the resolved 13# or d-compounds, and these in admixture with the corresponding lcompounds, particularly racemic mixtures. 13 - Ethyl - 3,17# - diacetoxygona - 1,3,5(10), 9(11)-tetraene is prepared from 13-ethylgona- 1,3,5(10),9(11) - tetraene - 3,17# - diol and acetic anhydride and is converted by hydroboration to a product of the invention, 13-ethylgona - 1,3,5(10) - triene - 3,11α,17# - triol, and a by-product, 13-ethylgona-1,3,5(10)-triene-3,9α, 17#-triol. 13 - Ethyl - 3,17 - diacetoxygona - 1,3,5(10), 9(11),16-pentaene is prepared from 13-ethyl-3- acetoxygona - 1,3,5(10),9(11) - tetraen - 17 - one and isopropenyl acetate. Other similar pentaene starting materials are prepared by a similar process. The steroids of the invention, which are stated to show hormonal effects, in particular metrotropic and adrenal corticoid type activity, may be made up into pharmaceutical compositions with suitable carriers.