p-Toluenesulfonic acid → HCID 86738866, compound

HRID 851292Notes

Reaction equation

HRID 851292 reaction equation
CC1C=CC(S(O)(=O)=O)=CC=1.[C:12]([C@:14]1([OH:35])[CH2:19][CH2:18][C@H:17]2[C@H:20]3[C:30](=[CH:31][CH2:32][C@:15]12[CH3:16])[C@:28]1([CH3:29])[C:23]([CH2:24][C:25](=[O:33])[CH2:26][CH2:27]1)=[C:22]([F:34])[CH2:21]3)#[CH:13]>C1COCC1>[C:12]([C@:14]1([OH:35])[CH2:19][CH2:18][C@H:17]2[C@H:20]3[C:30](=[CH:31][CH2:32][C@:15]12[CH3:16])[C@:28]1([CH3:29])[C:23](=[CH:24][C:25](=[O:33])[CH2:26][CH2:27]1)[C@@H:22]([F:34])[CH2:21]3)#[CH:13]

Participants

4

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 22823201HCID 22823201, compound

Product 1

HCID 86738866HCID 86738866, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

p-TSA (20 mg) is added to THF (5 ml) containing 17α-ethynyl-6-fluoro-17β-hydroxyandrost-5,9(11)-diene-3-one (VI, Example 5, 200 mg). After one hour at 20°-25°, the mixture is heated to reflux for 1.5 hrs. After cooling, the organic diluent is removed under reduced pressure. The residue is taken up in ethyl acetate, washed with aqueous sodium carbonate, the organic mixtures dried over sodium sulfate, and the organic diluent is removed under reduced pressure to give a solid. Filtration chromatography on silica dioxide (4 g), eluting with methylene chloride with increasing amounts of ethyl acetate, gives the title compound. Rf (ethyl acetate/hexane, 1/1)=0.7; NMR (CDCl3 +CD3OD) 0.8, 1.4, 2.6, 5.3, 5.7 and 6.1 δ.

Workup

  1. temperaturethe mixture is heated
  2. temperatureto reflux for 1.5 hrs
  3. temperatureAfter cooling
  4. customthe organic diluent is removed under reduced pressure
  5. washwashed with aqueous sodium carbonate
  6. dry with materialthe organic mixtures dried over sodium sulfate
  7. customthe organic diluent is removed under reduced pressure
  8. customto give a solid
  9. filtrationFiltration chromatography on silica dioxide (4 g)
  10. washeluting with methylene chloride with increasing amounts of ethyl acetate

Sources & evidence

ORD record
ord-eb7c2e17194c4d7bb7921db03d6e7079
Source dataset
uspto-grants-1983_05
Patent number
US04383947

Reaction notes

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