GB517307A - Manufacture of ketones of the cyclopentanopolyhydrophenanthrene series - Google Patents

Abstract

517,307. Cyclopentanophenanthrene ketones. SOC. OF CHEMICAL INDUSTRY IN BASLE. July 14, 1938, Nos. 11699/39, 11700/39, and 11701/39. Convention dates, July 14, 1937, June 9, 1938, and June 24, 1938. Divided out of 517,277. [Class 2 (iii)] Ketones of the cyclopentanopolyhydrophenanthrene series are obtained by reacting a compound of this series containing in the 17- position a carboxylic acid halide group or a side chain carrying a carboxylic acid halide group with a metal derivative of a compound of the formula x##CH-Z, where X represents a carbalkoxy, carboxylic amide or a nitrile group, Y represents an acyl, carbalkoxy, carboxylic amide or a nitrile group, and Z represents hydrogen or a hydrocarbon residue. Parent materials mentioned include saturated and unsaturated halide of aetio-cholenic acids such as 3-oxy-, 3-keto- and/or -17-oxy-aetiocholanic acids, 3-11-diketo- or 3-keto-11-oxy- and/or -17-oxy-aetio cholanic acids also corresponding compounds of the bisnorcholanic acid, cholane-17-acetic acid, norcholanic acid, or 3- carboxy-aetio-cholanic acid. The parent materials may in addition contain further substituents such as substituted or unsubstituted hydroxyl carbinol or cyclic keto groups and particularly such derivatives thereof such as enol esters and. enol ethers. Metal organic compounds specified include malonic acid esters, malonamide and malonitrile, analogous cyanacetic acid and acetoacetic acid derivatives and their substitution products and homologus containing for example alkali metals magnesium copper or aluminium. Instead of using an already prepared organic metal compound, the individual components of the compound may be used. The primary condensation products may, if desired, be saponified, subjected to ketone scission, acid scission and/or decarboxylated. In an example a benzene solution of #<4-5>-3 keto-aetiocholenic acid chloride is added to a suspension in alcohol of sodium malonic ester. The reaction solution is boiled under reflux the benzene removed, and the residue extracted with the ether to give #<4À5>-3-keto-pregnen-20- one-21-dicarboxylic acid ester. This is saponified with alcoholic alkali, extracted with ether and sublimed in vacuo to give pure #<4-5>- pregnene-3-ol-20-one. Instead of the acid chloride another acid halide may be used and instead of sodium malonic ester there may be used alkali compounds of malonitrile and malonamides or of derivatives of cyanoacetic acid and acetoacetic acid. Moreover, the 3-ketoaetio cholenic acid chloride may be replaced by an enol derivative such as the enol ester or the enol ether. The starting material may also be a 3-acyloxy aetio cholenic acid halide in which case Q <5>-<5>-pregnenol-(3)-one-(20) is analogously obtained.