Benzene → 17beta, 19-Dihydroxy-1alpha,7alpha-dimethyl-4-androsten-3-one diacetate

HRID 1733116Notes

Reaction equation

HRID 1733116 reaction equation
[C:1]([OH:4])(=[O:3])[CH3:2].[C:5]([OH:8])(=[O:7])[CH3:6].[OH:9][C@H:10]1[CH2:15][CH2:14][C@H:13]2[C@H:16]3[C@H:27]([CH2:28][CH2:29][C@:11]12[CH3:12])[C@:24]1([CH2:25][OH:26])[C:19](=[CH:20][C:21](=[O:31])[CH2:22][C@@H:23]1[CH3:30])[CH:18]=[CH:17]3.[CH3:32][Cu]C.[Li].[Cl-].[NH4+].C1C=CC=CC=1>O1CCCC1>[C:1]([OH:4])(=[O:3])[CH3:2].[C:5]([OH:8])(=[O:7])[CH3:6].[OH:9][C@H:10]1[CH2:15][CH2:14][C@H:13]2[C@H:16]3[C@H:27]([CH2:28][CH2:29][C@:11]12[CH3:12])[C@:24]1([CH2:25][OH:26])[C:19](=[CH:20][C:21](=[O:31])[CH2:22][C@@H:23]1[CH3:30])[CH2:18][C@H:17]3[CH3:32]

Participants

6

Reactant 4

HCID 241BenzeneHCID 25517Ammonium ChlorideHCID 8673474317beta, 19-Dihydroxy-1alpha-methyl-4,6-androstadien-3-one diacetateHCID 178477771HCID 178477771, compound

Product 1

HCID 8673474217beta, 19-Dihydroxy-1alpha,7alpha-dimethyl-4-androsten-3-one diacetate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 17β,19-dihydroxy-1α-methyl-4,6-androstadien-3-one diacetate in anhydrous tetrahydrofuran is added slowly to an ice cold ethereal solution of lithium dimethylcopper prepared as in the preceding Example. Stirring is continued for 30 minutes and the mixture is poured onto a saturated aqueous ammonium chloride solution. Benzene is added and the mixture filtered through a bed of diatomaceous earth. The organic layer is washed with aqueous ammonium chloride, water, dried over magnesium sulfate and evaporated to dryness. The residue is stirred at room temperature with aqueous methanolic hydrochloric acid for 1 hour and then poured onto ice water. The gum is extracted with ether, washed with water, dried over magnesium sulfate and the ether removed. The residue is chromatographed on silica gel and eluted with benzene. The eluant is recrystallized from hexane to give 17β,19-dihydroxy-1α,7α-dimethyl-4-androsten-3-one diacetate.

Workup

  1. filtrationthe mixture filtered through a bed of diatomaceous earth
  2. washThe organic layer is washed with aqueous ammonium chloride, water
  3. dry with materialdried over magnesium sulfate
  4. customevaporated to dryness
  5. stirringThe residue is stirred at room temperature with aqueous methanolic hydrochloric acid for 1 hour
  6. additionpoured onto ice water
  7. extractionThe gum is extracted with ether
  8. washwashed with water
  9. dry with materialdried over magnesium sulfate
  10. customthe ether removed
  11. customThe residue is chromatographed on silica gel
  12. washeluted with benzene
  13. customThe eluant is recrystallized from hexane

Sources & evidence

ORD record
ord-91644a05455c46b08df36e9fb1c4e538
Source dataset
uspto-grants-1980_12
Patent number
US04239681

Reaction notes

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