Smiles Rearrangement and O-Methylation of IIIc.-A solution of 160 mg of IIIc in 10 ml of Claisen alkali was allowed to stand for 10 min, acidified, and extracted with chloroform to give a partially rearranged product. The rearranged mixture was dissolved in 10 ml of tetrahydrofuran and stored for 24 hr at 5°with excess ethereal diazomethane. Evaporation of excess reagent and solvent gave a material which upon preparative thin layer chromatography in cyclohexane-ethyl acetate (1:1) gave 60 mg of a more polar compound identified as estra-l ,3,5(10)triene-2,3,11/3,17/3-tetrol 2-(2-benzoyl-4-nitro)phenyl ether 3methyl ether (IVa) [nmr 3.70 (s, 3-OCII3), 4.73 (m, H-lla)] and 28 mg of a less polar material identified as the isomeric 2methyl ether 3-(2-benzoyl-4-nitro)phenyl ether IVb [nmr 3.66 (s, 2-OCH3), 4.55 (m, H-lla)]. Neither of the two compounds could be obtained crystalline.2.3-Dihydroxyestra-l,3,5(10)-triene-l 1,17-dione 3-Methyl Ether (Vc).-To a solution of 30 mg of IVa in 10 ml of acetone Jones reagent was added dropwise until the orange-brown colorpersisted. The mixture was allowed to stand for 20 min at room temperature, poured into water, and extracted with chloroform. Following evaporation of the solvent, the noncrystalline product Va was homogenous according to thin layer chromatography in cyclohexane-ethyl acetate (1:1). A solution of the above oil in piperidine was refluxed for 2 hr and cooled, benzene was added, and the reaction mixture was washed well with 5% sulfuric acid. Drying and evaporation of solvent gave 8 mg of a semisolid Vc which crystallized from methanol: mp 135-140°; [a]n +129.7°; nmr 0.93 (s, C-18 CII3), 3.86 (s, 3-OCII3), 6.57 (s, H-l), and 6.62 (s, H-4).