Reaktion #93685

Reaktionsgleichung

phenylsulfonylchloride

Phenylsulfonylchloride

Trimethylamine

Hydrochloric acid

Phenylsulfonylchloride

17α-Acetyl-17β-hydroxy-6,16-dimethyleneandrosta-4-en-3-one

trimethylamine

→

6-Methylene-16-(phenylsulfinylmethyl)pregna-4,16-diene-3,20-dione

Lösungsmittel

methylene chloride

methylene chloride

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturcooled to -20°
2. 2
   Sonstigethe reaction approximately 80-85% complete
3. 3
   Sonstigethe reaction
4. 4
   Sonstigethe reaction
5. 5
   Sonstigenow being 7°
6. 6
   SonstigeThe phases are separated
7. 7
   ExtraktionThe aqueous portion is back-extracted with methylene chloride (10 ml)
8. 8
   WaschenThe organic extracts are washed with phosphate buffer (25 ml)
9. 9
   Extraktionback-extracted with methylene chloride (10 ml)
10. 10
    Sonstigedired over sodium sulfate overnight at 20°-25°
11. 11
    FiltrationThis mixture is filtered
12. 12
    Einengenthe filtrate concentrated under reduced pressure to an oil, which

Vorschrift

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.

Quelle