Abstract
A short step synthesis of estradiol was presented. 1-Vinyl-6-methoxy-1-tetralol (I) was condensed with 2-methyl-1, 3-cyclopentanedione (II)in the presence of Triton B to give dl-3-methoxy-8, 14-secoestra-1, 3, 5(10), 9-tetraene-14, 17-dione (III) which was converted by phosphorus pentoxide into the known dl-3-methoxyestra-1, 3, 5(10), 8, 14-pentaen-17-one(IV). The ketone (IV) was treated with sodium borohydride in methanol, yielding dl-3-methoxyestra-1, 3, 5(10), 8, 14-pentaen-17β-ol(V). Catalytic hydrogenation of this compound over Raney nickel was found to be stereospecific, yielding dl-3-methoxyestra-1, 3, 5, (10), 8-tetraen-17β-ol(VI). This compound was subjected to K-NH3reduction to give dl-estradiol 3-methyl ether (VII).Racemic V was resolved through its 17 l-menthoxyacetate and d-estradiol 3-methyl ether obtained by the above series of reactions was identical with the material of natural origin. dl-Equilenin 3-methyl ether was prepared from dl-3-methoxyestra-1, 3, 5(10), 8-tetraen-17β-ol (VI) by oxidation with Jones' reagent at one step.
