GB733448A - Steroid alkali-metal enolates - Google Patents

Abstract

The invention comprises 21-alkoxyoxalyl-11-ketoprogesterone alkali metal enolates of the general formula <FORM:0733448/IV (b)/1> wherein M represents an alkali metal and R represents an alkyl radical, and a process for the preparation thereof by mixing 11-ketoprogesterone with an alkyl diester of oxalic acid in the presence of a catalyst consisting of an alkali metal or an alkali metal base, and maintaining the temperature of the reaction mixture between about 0 DEG C. and the boiling point of the reaction mixture. The preferred compounds are those in which the alkyl radical of the alkoxy group contains from 1 to 8 carbon atoms inclusive, and those in which M represents sodium or potassium. The alkyl radicals of the diester of oxalic acid may each contain from 1 to 8 carbon atoms. The catalyst may be an alkali metal alkoxide, e.g. containing from 1 to 8 carbon atoms in the alkyl radical, a solution of an alkali metal in an alkanol the alkyl radical of which contains 1 to 8 carbon atoms, an alkali-metal hydride, sodium amide or triphenylmethyl sodium. About one molar equivalent of the catalyst may be used. The reaction may be carried out in an alkanol corresponding to the ester of the oxalic acid, or in an inert solvent such as benzene or ether. In the examples the following compounds are prepared: the sodium and potassium enolates of 21-methoxyoxalyl-and 21 - ethoxyoxalyl - 11 - keto - progesterone and the sodium enolate of 21-propoxyoxalyl-11-keto-progesterone, the catalyst used being sodium methoxide, potassium in tertiary butyl alcohol, sodium in methanol and in propanol, and sodium amide. Additional compounds referred to are the sodium and potassium enolates of 21 - butoxy -, 21 - amyloxy -, 21 - hexyloxy-, 21 - heptyloxy - and 21 - octyloxy - oxalyl - 11-keto-progesterones. 21 - Acetoxy - 11 - ketoprogesterone is obtained by reacting iodine in methanol with an enolate of the above general formula and then adding sodium methoxide in methanol to form 21-iodo-11-ketoprogesterone which is then reacted with acetic acid in the presence of potassium bicarbonate to form the 21-acetoxy radical.