Abstract 3α-Hydroxy-17-acetoxy-6α-methyl-5β-pregnan-20-one (IIIa) has been isolated from urine of patients receiving medroxyprogesterone acetate (MPA). It was characterized by partial synthesis from MPA by catalytic reduction with palladium-charcoal to 17-acetoxy-6α- methyl-5β-pregnan-3, 20-dione (IV) and reduction of the latter with sodum borohydride. The isolation of 6β, 17, 21-trihydroxy-6α-methyl-pregn-4-ene-3, 20-dione (IIc) is reported for ...