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

HRID 1834939Notes

Reaction equation

HRID 1834939 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 which is rapidly brought to its reflux temperature. The t-butanol is removed by distillation at atmospheric pressure at such a rate that the combined reflux and distillation time equals one hour. The dark pasty residue is triturated with hot chloroform and cooled. The solid is removed by filtration and the filtrate 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. This diene so prepared is dissolved in acetone and chilled in an ice bath. Jones reagent is added over a 10 minute period and stirring continued for an additional 45 minutes. The mixture is poured onto water. The solid is filtered and recrystallized from benzene to yield 4,6-androstadiene-3,17,19-trione.

Workup

  1. temperaturereflux temperature
  2. customThe t-butanol is removed by distillation at atmospheric pressure at such a rate that the
  3. temperaturecombined reflux
  4. distillationdistillation time equals one hour
  5. customThe dark pasty residue is triturated with hot chloroform
  6. temperaturecooled
  7. customThe solid is removed by filtration
  8. extractionthe filtrate 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-d71cc31f288c4af2a7de04a7e832a005
Source dataset
uspto-grants-1978_01
Patent number
US04071624

Reaction notes

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