Novel steroids of the formulae FORM:1070113/C2/1 (wherein R is a C2- 10 divalent aliphatic hydrocarbon radical separating the oxygen atoms by at least 2 carbon atoms; R1 is a C2- 10 divalent aliphatic hydrocarbon radical; OR1 is hydroxy, acyloxy or C1- 12 hydrocarbonoxy; R2 is H or methyl; R3 is H or acyl; Z is a saturated link or a 6,7-double bond; and X is C3- 10 isoalkyl, halogen, dialkylamino, carboxyl or cyano) are prepared by reacting the appropriate estrone derivative with a ketalizing diol, splitting the ketal by the method described in Specification 1,069,861, and, when required, reacting the obtained 17b -hydroxy-alkoxy steroids with tosyl chloride to give the tosylates and reacting these with alkali metal halides, dialkylamines or alkali metal cyanides and, when required, hydrolysing the obtained cyano-alkoxy steroids to the corresponding carboxy-alkoxy steroids, and, when required, treating these with alkyl magnesium halides, dehydrating the obtained tertiary alcohols and catalytically hydrogenating the dehydration products to obtain the required products wherein X is isoalkyl. Further products wherein X is OH may also be obtained by oxidation of the ols thus prepared to the corresponding ketones and reaction of these with Grignard reagents. Hydroxy groups may be acylated by standard procedures. The methyl ethers of 1-methyl-estrone, D 6-dehydroestrone, and 1-methyl-D 6-dehydroestrone are prepared from the 3-ols and methyl sulphate. The extratrienes of the invention, which are stated to have estrogenic activity, may be made up into pharmaceutical compositions with suitable carriers.
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