HCID 86738656, compound → HCID 86738657, compound

HRID 2199091Notes

Reaction equation

HRID 2199091 reaction equation
C([O:4][C@H:5]1[CH2:22][C@@:20]2([CH3:21])[C@@H:16]([CH2:17][CH2:18][C:19]2([S:26][CH2:27][CH2:28][CH2:29][CH3:30])[S:23][CH2:24][CH3:25])[C@H:15]2[C@@:6]1([F:33])[C@:7]1([CH3:32])[C:12]([CH2:13][CH2:14]2)=[CH:11][C:10](=[O:31])[CH:9]=[CH:8]1)(=O)C>CO.O1CCCC1>[CH2:27]([S:26][C:19]1([S:23][CH2:24][CH3:25])[CH2:18][CH2:17][C@H:16]2[C@H:15]3[C@:6]([F:33])([C@@H:5]([OH:4])[CH2:22][C@:20]12[CH3:21])[C@:7]1([CH3:32])[C:12](=[CH:11][C:10](=[O:31])[CH:9]=[CH:8]1)[CH2:13][CH2:14]3)[CH2:28][CH2:29][CH3:30]

Participants

4

Reactant 1

HCID 86738656HCID 86738656, compound

Product 1

HCID 86738657HCID 86738657, compoundYield 102.8%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

11β-Acetyloxy-17-(butylthio)-17-(ethylthio)-9-fluoroandrosta-1,4-diene-3-one (925 mg) is dissolved in a mixture of methanol (20 ml) and tetrahydrofuran (20 ml). The solution is stirred, purged with nitrogen and 3.0 M sodium hydroxide (3.0 ml) is added. After 2 hours a slight excess of acetic acid is added and the mixture is then concentrated in vacuo. It is diluted with water (150 ml) and extracted with chloroform. The chloroform extract is washed with water, dried (MgSO4 anh.) and evaporated to afford the title compound (870 mg). Examinations of the nmr spectrum and tlc behavior of this compound show the presence of some 17-(ethylthio)-9-fluoro-11β-hydroxyandrosta-1,4,16-triene-3-one and two 17-stereoisomers of the title compound. The material is applied on four 2.0 mm Merck silica gel plates and the plates are developed twice with chloroform-ethyl acetate (7:3). The products from the upper 1/3 and lower 2/3 of the broad band are isolated separately by extraction with chloroform-methanol (3:1 ) to afford respectively 340 and 527 mg of solids. One crystallization of the 340 mg of solid from ethyl acetate-hexane (1:1) and drying (100° C., 0.3 mm of Hg, 20 hours) gives the analytical specimen of the title compound (281 mg) melting point 118°-125° C. with consistent spectral data.

Workup

  1. custompurged with nitrogen and 3.0 M sodium hydroxide (3.0 ml)
  2. additionis added
  3. additionAfter 2 hours a slight excess of acetic acid is added
  4. concentrationthe mixture is then concentrated in vacuo
  5. additionIt is diluted with water (150 ml)
  6. extractionextracted with chloroform
  7. extractionThe chloroform extract
  8. washis washed with water
  9. dry with materialdried (MgSO4 anh.)
  10. customevaporated

Sources & evidence

ORD record
ord-e30c4713b8d548bf9d8372d58fba9be0
Source dataset
uspto-grants-1982_11
Patent number
US04361559

Reaction notes

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