Abstract: The present invention relates to a novel process for the preparation of 11.beta.-hydroxy-18-alkyl-estrane compounds by reacting an 11.beta.-hydroxy-13-methyl-gonane compound with an acylhypoiodite to give an 11.beta.-hydroxy-13-iodomethyl-gonane compound and reacting the latter compound with an alkylhalide in the presence of an alkali metal or with an alkali metal alkyl compound or with dimethylformamide in the presence of an alkali metal alkyl compound followed by a treatment with a proton donor, whereafter in the latter case the 18-methyl compound or is reacted with a trialkyl- or triaryl-alkylidene phosphorane (Wittig reagent), followed by a reduction of the thus-obtained 18-alkenyl compound to the corresponding 18-alkyl-compound, and to novel intermediates of the subject compounds.