Benzyl mercaptan → 17alpha-Benzylthio-1,4-Androstadiene-3,11-Dione

HRID 2052253Notes

Reaction equation

HRID 2052253 reaction equation
[Na].[CH2:2]([SH:9])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.CS(O[C@H:15]1[CH2:20][CH2:19][C@H:18]2[C@H:21]3[C@H:31]([C:32](=[O:34])[CH2:33][C@:16]12[CH3:17])[C@:29]1([CH3:30])[C:24](=[CH:25][C:26](=[O:35])[CH:27]=[CH:28]1)[CH2:23][CH2:22]3)(=O)=O>C(O)C>[CH2:2]([S:9][C@@H:15]1[CH2:20][CH2:19][C@H:18]2[C@H:21]3[C@H:31]([C:32](=[O:34])[CH2:33][C@:16]12[CH3:17])[C@:29]1([CH3:30])[C:24](=[CH:25][C:26](=[O:35])[CH:27]=[CH:28]1)[CH2:23][CH2:22]3)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 7509Benzyl mercaptanHCID 5360545SodiumHCID 5660910317beta-Methanesulfonyloxy-1,4-androstadiene-3,11-dione

Product 1

HCID 5663733817alpha-Benzylthio-1,4-Androstadiene-3,11-Dione

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To 13.8 gm. of sodium metal dissolved in 1040 ml. of ethanol is added 47 ml. of benzyl mercaptan, followed by 21 gm. of 17β-methanesulfonyloxy-1,4-androstadiene-3,11-dione. Heat to reflux for 72 hours, then cool and filter off insoluble material. Concentrate the filtrate in vacuo to about 150 ml. and precipitate into 1500 ml. of water containing 150 ml. of a 5% aqueous solution of sodium hypochlorite. Extract three times with 500 ml. portions of chloroform which is then washed twice with water. Dry the chloroform extracts over Na2SO4, then vacuum concentrate to dryness. Dissolve the residue in a minimum amount of chloroform/ethyl acetate (1:1) and pass through 300 gm. of silica gel. Take 1 l. fractions utilizing ethyl acetate/chloroform/hexane (1:10:10). Combine desired fractions as determined by thin layer chromatography and evaporate to dryness. Crystallize the resultant residue from ethyl acetate/hexane to obtain the title compound; m.p. 134°-136° C.; λmaxMeOH 237 nm (ε=17,100); [α]D26 +152.5° (DMF).

Workup

  1. temperatureHeat
  2. temperatureto reflux for 72 hours
  3. temperaturecool
  4. filtrationfilter off insoluble material
  5. concentrationConcentrate the filtrate in vacuo to about 150 ml
  6. extractionExtract three times with 500 ml
  7. washportions of chloroform which is then washed twice with water
  8. dry with materialDry the chloroform
  9. concentrationvacuum concentrate to dryness
  10. dissolutionDissolve the residue in a minimum amount of chloroform/ethyl acetate (1:1)
  11. customevaporate to dryness
  12. customCrystallize the resultant residue from ethyl acetate/hexane

Sources & evidence

ORD record
ord-59500d7995f34923bb970c0be65bb5d4
Source dataset
uspto-grants-1980_01
Patent number
US04183924

Reaction notes

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