Water → HCID 70400827, compound

HRID 371058Notes

Reaction equation

HRID 371058 reaction equation
[CH2:1]([SH:3])[CH3:2].C([O:7][C@H:8]1[CH2:25][C@@:23]2([CH3:24])[C@@H:19]([CH2:20][CH2:21][C@@H:22]2OS(C)(=O)=O)[C@H:18]2[C@@:9]1([F:33])[C@:10]1([CH3:32])[C:15]([CH2:16][CH2:17]2)=[CH:14][C:13](=[O:31])[CH:12]=[CH:11]1)(=O)C.O>CN(C)C=O>[CH2:1]([S:3][C@@H:22]1[CH2:21][CH2:20][C@H:19]2[C@H:18]3[C@:9]([F:33])([C@@H:8]([OH:7])[CH2:25][C@:23]12[CH3:24])[C@:10]1([CH3:32])[C:15](=[CH:14][C:13](=[O:31])[CH:12]=[CH:11]1)[CH2:16][CH2:17]3)[CH3:2]

Participants

5

Reactant 3

HCID 962Water2×HCID 6343EthanethiolHCID 86740192HCID 86740192, compound

Product 1

HCID 70400827HCID 70400827, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A suspension of 50% sodium hydride-paraffin (300 mg, 6.5 mmole) in dry dimethylformamide (20 ml) was cooled and stirred in an ice-water bath and ethanethiol (0.67 ml, 9.0 mmole) was added. The ice bath was then removed and the mixture was stirred at room temperature until a clear solution resulted. Then, (11β,17β)-11-(acetyloxy)-9-fluoro-17-(methanesulfonyloxy)androsta-1,4-dien-3-one (540 mg, 1.21 mmole) was added. The resulting solution was heated in a bath at 110°-120° C. under an atmosphere of nitrogen for 5.0 hours. After cooling to room temperature, water (1.0 ml) was added and the mixture was stirred for 20 minutes. The mixture was then added into water (150 ml) and was extracted with chloroform (3×50 ml). The extracts were combined, washed with water, dried (anhydrous magnesium sulfate) and evaporated to afford the title compound as a solid contaminated with paraffin. It was dissolved in chloroform-hexane (7:3; 20 ml) and absorbed on a column of silica gel (15 g). The column was then successively eluted with chloroform and chloroform:ethyl acetate (85:15) to afford the homogeneous (tlc) title compound as a solid (380 mg) from the later fractions. One crystallization from ethyl acetate-hexane followed by drying (110° C., 0.3 mm of Hg, 6 hours) gave the analytical specimen (362 mg), melting point 196°-197° C. with consistent spectral data.

Workup

  1. temperaturewas cooled
  2. customThe ice bath was then removed
  3. stirringthe mixture was stirred at room temperature until a clear solution
  4. customresulted
  5. temperatureThe resulting solution was heated in a bath at 110°-120° C. under an atmosphere of nitrogen for 5.0 hours
  6. stirringthe mixture was stirred for 20 minutes
  7. extractionwas extracted with chloroform (3×50 ml)
  8. washwashed with water
  9. dry with materialdried (anhydrous magnesium sulfate)
  10. customevaporated

Sources & evidence

ORD record
ord-18f4870aeb194a9889832ed0ee1b43ad
Source dataset
uspto-grants-1985_07
Patent number
US04529548

Reaction notes

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