Chloranil → HCID 86734740, compound

HRID 1390754Notes

Reaction equation

HRID 1390754 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:30])[CH2:22][CH2:23]1)[CH2:18][CH2:17]3.C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>C(O)(C)(C)C>[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:30])[CH2:22][CH2:23]1)[CH:18]=[CH:17]3

Participants

4

Reactant 2

HCID 8371ChloranilHCID 86734741HCID 86734741, compound

Product 1

HCID 86734740HCID 86734740, compound

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

17β,19-Dihydroxy-4-androsten-3-one diacetate 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 total reflux and distillation time equals 1 hour. The dark residue which remains is triturated with hot chloroform and filtered. The filtrate is extracted with water, a 2% sodium hydroxide solution, again with water, dried over magnesium sulfate and the solvent removed by evaporation to yield 17β,19-dihydroxy-4,6-androstadiene-3-one diacetate. The diene so prepared is refluxed with dichlorodicyanobenzoquinone in anhydrous dioxane for about 48 hours. The mixture is cooled, filtered and the filtrate poured onto a mixture of methylenechloride and water. The organic layer is separated, washed with water, dried well over magnesium sulfate and the solvent removed. The dark residue which remains is chromatographed on a silica gel column and eluted with methylenechloride. The eluate yields the desired 17β,19-dihydroxy-1,4,6-androstatrien-3-one diacetate.

Workup

  1. temperaturereflux temperature
  2. customThe t-butanol is removed by distillation at atmospheric pressure at such a rate that the
  3. temperaturetotal reflux
  4. distillationdistillation time equals 1 hour
  5. customThe dark residue which remains is triturated with hot chloroform
  6. filtrationfiltered
  7. extractionThe filtrate is extracted with water
  8. dry with materiala 2% sodium hydroxide solution, again with water, dried over magnesium sulfate
  9. customthe solvent removed by evaporation

Sources & evidence

ORD record
ord-a7f4dbfa5f99435d8e5c73a1c495eba1
Source dataset
uspto-grants-1979_02
Patent number
US04139617

Reaction notes

Loading…