Chloranil → 19-Hydroxy-4,6-androstadiene-3,17-dione

HRID 371851

Reaction equation

HRID 371851 reaction equation
[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH2:10][CH2:9][C:8]1=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]2.C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>C(O)(C)(C)C>[OH:1][CH2:2][C@@:3]12[C@@H:20]3[C@H:11]([C@H:12]4[C@@:16]([CH2:18][CH2:19]3)([CH3:17])[C:15](=[O:21])[CH2:14][CH2:13]4)[CH:10]=[CH:9][C:8]1=[CH:7][C:6](=[O:22])[CH2:5][CH2:4]2

Participants

4

Reactant 2

HCID 8371ChloranilHCID 25237919-Hydroxyandrostenedione

Product 1

HCID 5428584419-Hydroxy-4,6-androstadiene-3,17-dione

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

19-Hydroxy-4-androstene-3,17-dione and chloranil are dissolved in t-butanol and rapidly brought to reflux. The t-butanol is removed by distillation at atmospheric pressure at such a rate so that the total reflux and distillation time equals one hour. The dark pasty residue is triturated with hot chloroform and cooled. The solid which remains is removed by filtration and the filtrate successively extracted with water, a 2% sodium hydroxide solution and again with water. The organic layer is dried over magnesium sulfate and the solvent removed under vacuum to yield 19-hydroxy-4,6-androstadiene-3,17-dione. The diene so prepared is dissolved in acetone and chilled in an ice bath. Jones reagent is added over a period of about 10 minutes and stirring continued for an additional 45 minutes. The mixture is poured onto water. The solid which forms is filtered and recrystallized from benzene to yield 4,6-androstadiene-3,17,19-trione.

Workup

  1. temperatureto reflux
  2. customThe t-butanol is removed by distillation at atmospheric pressure at such a rate so that the
  3. temperaturetotal reflux
  4. distillationdistillation time equals one hour
  5. customThe dark pasty residue is triturated with hot chloroform
  6. temperaturecooled
  7. customThe solid which remains is removed by filtration
  8. extractionthe filtrate successively extracted with water
  9. dry with materialThe organic layer is dried over magnesium sulfate
  10. customthe solvent removed under vacuum

Sources & evidence

ORD record
ord-2d625556eb3e4ec295d382f39f9457ff
Source dataset
uspto-grants-1978_05
Patent number
US04087524

Linked notes

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