1,1,1,3,3,3-hexachloropropan-2-one

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:1.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 5,6β-epoxy-7β-hydroxy-15β,16β-methylen-3β-pivaloyloxy-5β-androstan-17-one (1.66 g, 0.004 mol) in dichloromethane (8 mL) is treated with hexachloroacetone (2 mL, 0.013 mol) and cooled to 0-2° C. Triphenylphosphine (1.53 g, 0.0044 mol) in dichloromethane (4 mL) is added dropwise and the mixture is stirred for one hour at 3-4° C., then for an additional hour at 10-15° C. at 10-15° C.

反応条件: temp:12.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: reaction of compound 2 with hexachloroacetone in dichloromethane added with triphenylphosphine at a temperature of 0-5° C. followed by heating to 10-15° C., to yield 7α-chloro-5,6β-epoxy-15β,16β-methylen-3β-pivaloyloxy-5β-androstan-17-one 3:

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3-methyl-3-(phenylmethylthio)butanoic acid (1 g, 4.6 mmol) and hexachloroacetone were dissolved in CH2Cl2 (20 mL) and cooled to −78° C. Triphenyl phosphine was added and the mixture was stirred for 30 minutes. Hydroxyethyl piperazine (550 μL, 4.5 mmol) was added in CH2Cl2 (10 mL) dropwise. Triethylamine (630 μL, 4.5 mmol) was added in CH2Cl2 (10 mL) dropwise. The cold bath was removed and the solution was stirred for 24 hours. The solvent was evaporated. The crude mixture was poured into 1N HCl (100 mL) and washed with Et2O (2×50 mL). The aqueous layer was made basic with 10% K2CO3 in a brine solution. The product was extracted with EtOAc (3×100 mL), dried over Na2SO4, and concentrated. This gave the title compound which was used immediately in the next reaction. 1H NMR (300 MHz, CDCl3) δ 7.18-7.37 (mult, 5H), 3.8 (s, 2H), 3.6 (t, J=5 Hz, 4H), 3.4 (t, J=5 Hz, 2H), 2.45-2.65 (mult, 8H), 1.5 (s, 6H). The cold bath was removed the solution was stirred for 24 hours The solvent was evaporated The crude mixture was poured into 1N HCl (100 mL) washed with Et2O (2×50 mL) The product was extracted with EtOAc (3×100 mL) dried over Na2SO4 concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 7.6 mL (54.2 mmol) of diisopropylamine in 100 mL of dry THF was cooled to -78° C. under argon, treated with 20.5 mL (47.2 mmol) of 2.3M n-butyllithium, and stirred for 15 minutes. To this solution was added a solution of 10.3 g (45.0 mmol) of 2-(2,4,5-trifluorophenyl)-4, 4-dimethyl-2-oxazoline in 100 mL of dry THF. The reaction mixture was stirred at -78° C. for 45 minutes. To this mixture was added 26.5 g (100 mmol) of hexachloroacetone, and the solution was warmed to room temperature. Water was added; the organic phase was washed with water, 1N hydrochloric acid, and 5% sodium bicarbonate, and was dried over magnesium sulfate. Concentration gave a dark oil which was chromatographed on silica gel to give 7.05 g of the title compound as a yellow oil. The reaction mixture was stirred at -78° C. for 45 minutes the organic phase was washed with water, 1N hydrochloric acid, and 5% sodium bicarbonate was dried over magnesium sulfate Concentration gave a dark oil which was chromatographed on silica gel

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of 800 mg of 11α-hydroxy-7α-methylestr-4-ene-3,17-dione (F) in 8 ml of dichloromethane was mixed at 0° C. with 1.21 ml of hexachloroacetone and 764 mg of triphenylphosphine and stirred at room temperature for 4 hours. Then, it was diluted with dichloromethane, washed neutral, dried on sodium sulfate, concentrated by evaporation in a vacuum and chromatographed on silica gel with hexane/ethyl acetate. 430 mg of pure 11β-chloro-7α-methyl-estr-4-ene-3,17-dione (F′) with a melting point of 215.1° C. was obtained ([α]D20=+182.7° (c=0.5% in chloroform)). washed neutral dried on sodium sulfate concentrated by evaporation in a vacuum chromatographed on silica gel with hexane/ethyl acetate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of trans-1-hydroxy-4-(tert-butoxycarbonylamino)-2-cyclohexene (2.93 g, 13.8 mmol) in hexachloroacetone (70 mL) was added triphenylphosphine (7.51 g, 28.6 mmol) and the mixture was stirred at room temperature for 1 hour. The mixture was concentrated and the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate) and provided 1.98 g (62%) of cis-1-(tert-butoxycarbonylamino)-4-chloro-2-cyclohexene as a yellow solid. The mixture was concentrated the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of trans-1-hydroxy-4-(tert-butoxycarbonylamino)-2-cyclohexene (2.93 g, 13.8 mmol) in hexachloroacetone (70 mL) was added triphenylphosphine (7.51 g, 28.6 mmol) and the mixture was stirred at room temperature for 1 hour. The mixture was concentrated and the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate) and provided 1.98 g (62%) of cis-1-(tert-butoxycarbonylamino)-4-chloro-2-cyclohexene as a yellow solid. The mixture was concentrated the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a mixture of trans-1-hydroxy-4-(tert-butoxycarbonylamino)-2-cyclohexene (2.93 g, 13.8 mmol) in hexachloroacetone (70 mL) was added triphenylphosphine (7.51 g, 28.6 mmol) and the mixture was stirred at room temperature for 1 hour. The mixture was concentrated and the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate) and provided 1.98 g (62%) of cis-1-(tert-butoxycarbonylamino)-4-chloro-2-cyclohexene as a yellow solid. The mixture was concentrated the thus obtained oil was purified by column chromatography on silica gel (10:1 hexanes-ethyl acetate)

反応条件: temp:140.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A 2-liter round bottom flask equipped with a condenser and mechanical stirrer was charged with 1 liter (6.6 moles) of hexachloroacetone, 411.2 g (2.2 moles) of anhydrous antimony trifluoride and 30 ml of antimony pentachloride. The mixture was heated to 140° C. for a period of one hour then cooled to 0° C. The liquid portion of the reaction was decanted from the salts of the reaction and washed with 5×200 ml portions of 12N HCl dried over MgSO4 and distilled. The fraction boiling at 160°-167° C. afforded 700 g of product as a 3:1 mixture of pentachlorofluoro and tetrachlorodifluoro acetones, respectively, and was used without further purification. A 2-liter round bottom flask equipped with a condenser and mechanical stirrer then cooled to 0° C The liquid portion of the reaction was decanted from the salts of the reaction washed with 5×200 ml portions of 12N HCl dried over MgSO4 distilled