Ammonium Chloride → HCID 54065673, compound

Participants

Reaction Steps

300 mg of CuCl were added to the Grignard reagent prepared from 4.5 g of 4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl bromide and 0.8 g of Mg in 15 ml of dry tetra-hydrofuran, followed by 2.2 g of (5α,10α,14β,17α)-3,3-ethylenedioxy-5,10-epoxyoestr-9(11)-en-17-ol, prepared in Example 3, in 10 ml of dry tetrahydrofuran. After stirring for 1 hour at room temperature, the mixture was poured into 200 ml of saturated NH4Cl solution. After extraction with ethyl acetate and washing, drying and concentrating the organic phase, the residue was chromatographed on silica gel using hexane/ethyl acetate 1/1 as eluent. After crystallization from diisopropyl ether, 1.7 g of (5α,11β,14β,17α)-3,3-ethylenedioxy-11[4-(5,5-dimethyl-1,3-dioxan-2-yl) phenyl]oestr-9-ene-5,17-diol were obtained; melting point: 176°-177° C. A solution of 1.5 g of this compound in 30 ml of 80% acetic acid was heated for 45 min. at 75° C. After cooling and neutralizing by concentrated NH4OH, the product was extracted with ethyl acetate. The organic phase was washed, dried and concentrated. The residue was chromatographed on silica gel using hexane/ethyl acetate 1/1 as eluent. After crystallization from diisopropyl ether, 0.6 g of (11β,14β,17α)-11-(4-formylphenyl)-17-hydroxyoestra-4,9-dien-3-one was obtained; melting point: 153°-155° C.

Provenance & Evidence