GB1070943A - 13-alkylgonanes and 13-alkyl-d-homogonanes - Google Patents

Abstract

In esterification (including transesterification) processes in which a metal or a metal compound is used as a catalyst, the catalyst is separated from the esterification product by treating the product with activated carbon at a temperature not exceeding 200 DEG C. Part or all of any unused alcohol may be separated from the esterification product before the treatment with carbon. Also, the catalyst may first be converted into a different form, e.g. by precipitating a titanium or zirconium compound by means of lime. The process is particularly applicable to the treatment of products obtained by esterifying phythalic anhydride with an alcohol or mixture of alcohols containing 4-14 carbon atoms produced by the "OXO" process, and comparative experimental results are given of the esterification of phthalic anhydride with iso-octanol (produced by the "OXO" process) in the presence of the titanium tetra-alkoxide of iso-octanol as a catalyst. A number of other metals which may constitute the catalyst or from which the catalyst may be derived are specified.ALSO:The invention comprises compounds of formula <FORM:1070943/C2/1> wherein R1 is a C2-4 n-alkyl group, Y is a carbonyl, ketalized carbonyl, hydroxymethylene or acryloxymethylene group or a group -CR2OR- wherein R2 is an alkyl, alkenyl or alkynyl group transto R1 and -OR ia s hydroxy or acyloxy group cisto R1, Q is a methylene or ethylene group, the hydrogen atoms at the 14, 8 and 9 positions are transanti-, transwith respect to the group R1 and the hydrogen atom at the 10-position is antito that at the 9-position, including racemates of the 13b - and 13a -enantiomers, and their preparation by (a) treatment of a 3-ketone with a mixture of lithium/aluminium/hydride and aluminium chloride, (b) treatment of a 3-thioketal with deactivated Raney nickel or with an alkali metal or alkaline earth metal in liquid ammonia, (c) treatment of a 3-keto, hydroxy, alkoxy, acyloxy, chloro- or bromo-compound with an alkali or alkaline earth metal in liquid ammonia or an aliphatic primary amine, or with lithium aluminium hydride alone or in the presence of aluminium chloride, (d) oxidation, reduction, ketalization, esterification or hydrolysis of the group Y, (e) reaction of a carbonyl group Y with an organometallic reagent, or (f) reduction of the 4,5 double bond. 3-Thioketal starting materials are prepared by reaction of a 3-ketone with a thiol or dithiol in the presence of zinc chloride or boron trifluoride etherate. (\sB) 3 - Acetoxy - 13b , 17a - diethyl - gon - 4-en-17b -ol is prepared by reduction of the corresponding 3-ketone with lithium aluminium hydride to form the 3-ol, followed by acylation. The compounds of the invention have anabolic, progestational and anti-estrogenic activity and may be used in pharmaceutical compositions in combination with a carrier, for example, in forms suitable for oral, parenteral or rectal administration.