(8R,9S,10R,13S,14S)-13-methyl-1,2,6,7,8,9,10,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthrene-3,17-dione

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2). The reaction mixture was concentrated under reduced pressure the residue was triturated with dichloromethane The solid was removed by filtration the filtrate was concentrated to give a brown gum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ 0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2). The reaction mixture was concentrated under reduced pressure the residue was triturated with dichloromethane The solid was removed by filtration the filtrate was concentrated to give a brown gum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ 0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2). The reaction mixture was concentrated under reduced pressure the residue was triturated with dichloromethane The solid was removed by filtration the filtrate was concentrated to give a brown gum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ 0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2). The reaction mixture was concentrated under reduced pressure the residue was triturated with dichloromethane The solid was removed by filtration the filtrate was concentrated to give a brown gum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A water-jacketed glass column of 2.7 cm inner diameter is packed with a suspension of 50.0 g of basic alumina (sold by Shokubai Kasei Kogyo Co. Ltd. under trade name of ACBR-3, calcined at a temperature above 500° C. and pulverized to about 50 mesh) in 100 ml of 1,2-dichloroethane (to a depth of 13.0 cm) and water is passed through the jacket so as to set the temperature at 20° C. In 1400 ml of 1,2-dichloroethane, 20.00 g of crude 19-norethisterone of 91.8% purity which results from ethynylation of 19-norandrost-4-ene-3,17-dione and which contains 1.7% ethynylestradiol in addition to other impurities is dissolved at 20° C. and the resulting solution is introduced on the top of the column at a linear velocity of 2 m/hr using a feed pump. The 1,2-dichloroethane solution passed through the alumina is received in an Erlenmeyer flask. After the solution of 19-norethisterone in 1,2-dichloroethan has been passed, 500 ml of 1,2-dichloroethane is further passed through the alumina to wash it. The two liquids are combined and concentrated to dryness at reduced pressure with 1,2-dichloroethane being distilled off. calcined at a temperature above 500° C. at 20° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of dione 53 (5.0 g, 18.36 mmol) and chloranil (5.4 g, 22 mmol) in dry ethanol (500 mL) was stirred at 60-65° C. for 2 h. The reaction mixture was concentrated under reduced pressure, and the residue was triturated with dichloromethane. The solid was removed by filtration, and the filtrate was concentrated to give a brown gum. Chromatography (20% EtOAc/hexane) yielded crude dione 54 as a yellow solid (2.3 g, 46%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.78 (s, 1), 6.25 (m, 2). The reaction mixture was concentrated under reduced pressure the residue was triturated with dichloromethane The solid was removed by filtration the filtrate was concentrated to give a brown gum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 19-nortestosterone 52 (26.85 g, 97.85 mmol) in acetic acid (200 mL) was added a CrO3 (7.4 g, 74 mmol) in acetic acid (150 mL) and stirred for 1 h at room temperature. The reaction mixture was concentrated under reduced pressure to half of its initial volume, poured into 1 M hydrochloric acid (500 mL) and extracted with EtOAc. The combined organic layers were washed with saturated aqueous NaHCO3, dried over anhydrous MgSO4, filtered, and then concentrated to afford dione 53 as a white solid (25.3 g, 95%): 1H NMR (300 MHz, CDCl3) δ0.94 (s, 3, CH3), 5.85 (s, 1). The reaction mixture was concentrated under reduced pressure to half of its initial volume poured into 1 M hydrochloric acid (500 mL) extracted with EtOAc The combined organic layers were washed with saturated aqueous NaHCO3 dried over anhydrous MgSO4 filtered concentrated