Réaction #93685

ord-07dad5d65ceb4deab29eed308f16bb51

Conditions de réaction

Conditions détaillées
See reaction.notes.procedure_details.

Traitement

  1. 1
    Températurecooled to -20°
  2. 2
    Autrethe reaction approximately 80-85% complete
  3. 3
    Autrethe reaction
  4. 4
    Autrethe reaction
  5. 5
    Autrenow being 7°
  6. 6
    AutreThe phases are separated
  7. 7
    ExtractionThe aqueous portion is back-extracted with methylene chloride (10 ml)
  8. 8
    LavageThe organic extracts are washed with phosphate buffer (25 ml)
  9. 9
    Extractionback-extracted with methylene chloride (10 ml)
  10. 10
    Autredired over sodium sulfate overnight at 20°-25°
  11. 11
    FiltrationThis mixture is filtered
  12. 12
    Concentrationthe filtrate concentrated under reduced pressure to an oil, which

Mode opératoire

17α-Acetyl-17β-hydroxy-6,16-dimethyleneandrosta-4-en-3-one (Example 5, 8.0 g) is dissolved in methylene chloride (66 ml) and cooled to -20°. Trimethylamine (2.56 ml) at -20° and methylene chloride (5 ml) are mixed and the trimethylamine mixture transferred by syringe to the steroid solution. To the cold steroid solution was added phenylsulfonylchloride (1.0 equivalent) by a syringe pump over 1 hr. TLC shows the reaction approximately 80-85% complete. Phenylsulfonylchloride (0.25 equivalent) was added over approximately 10 min., TLC showing the reaction to be approximately 95% complete. Phenylsulfonylchloride (0.10 equivalent) was then added for a total of 1.35 equivalence, at which time TLC shows the reaction to be complete. Hydrochloric acid (10%, 40 ml) was added all at once, the temperature now being 7°, and the mixture stirred for about 10 min. The phases are separated. The aqueous portion is back-extracted with methylene chloride (10 ml). The organic extracts are washed with phosphate buffer (25 ml) and back-extracted with methylene chloride (10 ml). The organic extracts are combined, dired over sodium sulfate overnight at 20°-25°. This mixture is filtered and the filtrate concentrated under reduced pressure to an oil, which is the title compound.

Source

DOI: 10.6084/m9.figshare.5104873.v1Brevet: US04614621uspto-grants-1986_09