Methanethiol → HCID 70400756, compound

HRID 371057Notes

Reaction equation

HRID 371057 reaction equation
[CH3:1][SH:2].C([O:6][C@H:7]1[CH2:24][C@@:22]2([CH3:23])[C@@H:18]([CH2:19][CH2:20][C@@H:21]2OS(C)(=O)=O)[C@H:17]2[C@@:8]1([F:32])[C@:9]1([CH3:31])[C:14]([CH2:15][CH2:16]2)=[CH:13][C:12](=[O:30])[CH:11]=[CH:10]1)(=O)C.O>CN(C)C=O>[F:32][C@:8]12[C@@H:7]([OH:6])[CH2:24][C@@:22]3([CH3:23])[C@@H:18]([CH2:19][CH2:20][C@H:21]3[S:2][CH3:1])[C@@H:17]1[CH2:16][CH2:15][C:14]1[C@:9]2([CH3:31])[CH:10]=[CH:11][C:12](=[O:30])[CH:13]=1

Participants

5

Reactant 3

HCID 878MethanethiolHCID 962Water2×HCID 86740192HCID 86740192, compound

Product 1

HCID 70400756HCID 70400756, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a suspension of 50% sodium hydride/paraffin (100 mg) in dry dimethylformamide (10 ml), cooled and stirred in an ice bath, a stream of methanethiol was passed until a homogeneous solution resulted. (11β,17β)-11-(Acetyloxy)-9-fluoro-17-(methanesulfonyloxy)androsta-1,4-dien-3-one (280 mg, 0.64 mmole) was added and the solution was heated in an atmosphere of nitrogen in a bath at 100°-120° C. for 5.0 hours. The mixture was then cooled to room temperature and water (1.0 ml) was added. After stirring for 20 minutes, the mixture was poured into water and was extracted with chloroform. The chloroform solution was washed with water, dried (anhydrous magnesium sulfate) and evaporated in vacuo. The residue was dissolved in chloroform-hexane (7:3; 15 ml) and absorbed on a column of silica gel (5.0 g). The column was first eluted with chloroform to remove the paraffin. Further elution of the column with chloroform: hexane (9:1) gave the title compound (179 mg) which had a small amount of a slightly less polar impurity (tlc). One crystallization of this from ethyl acetate followed by drying (110° C., 0.3 mm of Hg, 20 hours) gave the analytical specimen (157 mg), melting point 235°-236° C. with consistent spectral data.

Workup

  1. temperaturecooled
  2. customresulted
  3. temperaturethe solution was heated in an atmosphere of nitrogen in a bath at 100°-120° C. for 5.0 hours
  4. stirringAfter stirring for 20 minutes
  5. extractionwas extracted with chloroform
  6. washThe chloroform solution was washed with water
  7. dry with materialdried (anhydrous magnesium sulfate)
  8. customevaporated in vacuo
  9. dissolutionThe residue was dissolved in chloroform-hexane (7:3; 15 ml)
  10. customabsorbed on a column of silica gel (5.0 g)
  11. washThe column was first eluted with chloroform
  12. customto remove the paraffin
  13. washFurther elution of the column with chloroform: hexane (9:1)

Sources & evidence

ORD record
ord-5cf18dadac2a49378acc2353b05658f4
Source dataset
uspto-grants-1985_07
Patent number
US04529548

Reaction notes

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