反应详情

温度

74.5 °C

A suspension of methyltriphenylphosphonium bromide (100.03 g, 0.28001 mol) and potassium t-butoxide (31.42 g, 0.2800 mol) in anh. dimethylsulfoxide (DMSO, 320 mL) under argon was stirred in an oil bath (68-81° C.) 1 h, after which estrone (15.14 g, 55.99 mmol) in anh. DMSO (320 mL) was added via syringe. See FIG. 17. Stirring was continued 1 h and the reaction allowed to cool. The mixture was poured into 800 mL of ice-1 N hydrochloric acid and then extracted three times with 400 mL aliquots of ether. The combined organic extracts were washed with 350 mL of saturated sodium bicarbonate+400 mL of brine, dried over sodium sulfate, and flash filtered through a 58 mm high×84 mm dia. column of silica gel (200-40 mesh). Product continued eluting with additional ether. Concentration of appropriate fractions under reduced pressure and three-fold recrystallization from aqueous ethanol gave very fine white needles (11.47 g, 42.73 mmol, 76%), m.p. 134-136° C., homogeneous to TLC (20% ethyl acetate/hexanes on silica gel, Rf 0.45).

1. stirringStirring
2. waitwas continued 1 h
3. temperatureto cool
4. extractionextracted three times with 400 mL aliquots of ether
5. washThe combined organic extracts were washed with 350 mL of saturated sodium bicarbonate+400 mL of brine
6. dry with materialdried over sodium sulfate, and flash
7. filtrationfiltered through a 58 mm high×84 mm dia
8. washProduct continued eluting with additional ether
9. customConcentration of appropriate fractions under reduced pressure and three-fold recrystallization from aqueous ethanol