A process for the production of medrogestone, in which, in an intermediate step, the solvate 3.beta.,5.alpha.,6.beta.-trihydroxy-6.alpha.,17.alpha.-dimethylpregnan-20-one monomethanolate is obtained as a solid, stable compound by displacing the organic solvent from a solution of of 3.beta.,5.alpha.,6.beta.-trihydroxy-6.alpha.,17.alpha.-dimethylpregnan-20-one with a lower alkanol, and a Diels-Alder adduct of 6-methylene-17.alpha.-methylpregn-4-ene-3,20-dione with maleic anhydride is used as an intermediate for production of the corresponding dicarboxylic acid salt for removal of 6-methylene-17.alpha.-methylpregn-4-ene-3,20-dione contamination of the desired product. Another intermediate, 6.beta.-hydroxy-6.alpha.,17.alpha.-dimethylpregn-4-ene-3,20-dione, has been found to prevent smooth muscle proliferation and is useful in the treatment of atherosclerosis and restinosis.