Water → 17-Cyano-9,17-dihydroxyandrost-4-ene-3-one

HRID 1650077Notes

Reaction equation

HRID 1650077 reaction equation
S(=O)(=O)(O)O.[OH:6][C@:7]12[CH2:24][CH2:23][C@@:21]3([CH3:22])[C@@H:17]([CH2:18][CH2:19][C:20]3=[O:25])[C@@H:16]1[CH2:15][CH2:14][C:13]1[C@:8]2([CH3:27])[CH2:9][CH2:10][C:11](=[O:26])[CH:12]=1.[C-:28]#[N:29].[K+].O>CO>[CH3:22][C@@:21]12[C:20]([OH:25])([C:28]#[N:29])[CH2:19][CH2:18][C@H:17]1[C@@H:16]1[CH2:15][CH2:14][C:13]3[C@@:8]([CH3:27])([C:7]1([OH:6])[CH2:24][CH2:23]2)[CH2:9][CH2:10][C:11](=[O:26])[CH:12]=3

Participants

6

Reactant 4

HCID 962Water3×HCID 1118Sulfuric Acid2×HCID 9032Potassium CyanideHCID 104250179alpha-Hydroxyandrost-4-ene-3,17-dione

Product 1

HCID 308277817-Cyano-9,17-dihydroxyandrost-4-ene-3-one

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Sulfuric acid (2.07 ml) is added to 9α-hydroxyandrost-4-ene-3,17-dione (I, 21.14 g) and potassium cyanide (6.70 g) slurried in methanol (71.5 ml) and water (6.8 ml) at <5°. The mixture is allowed to warm to 15° over 0.5 hr, then warmed to 30° over 1 hr. The mixture is stirred at 30° for 2.5 hr, then cooled to 2° and sulfuric acid (0.32 ml) is added. The mixture is then stirred at 30° for 2 hr and water (13 ml) is added. Next, water (52 ml) is added over 12 hr, maintaining the mixture at 30°. The mixture is stirred 5 hr at 30°, then cooled to 0° and quenched with sulfuric acid (1 ml). Methanol (89 ml) is added and the mixture is heated to 55°. The solvent is then removed by reduced pressure until the boiling point begins to rise rapidly. The mixture is then cooled to 32° and water (105 ml) is added over 12 min. The mixture is further cooled to 0° and the the solids are collected by vacuum filtration and washed with water to give the title compound, mp 230°-233° (with decomposition). ##STR1##

Workup

  1. customat <5°
  2. temperatureto warm to 15° over 0.5 hr
  3. temperaturewarmed to 30° over 1 hr
  4. temperaturecooled to 2°
  5. stirringThe mixture is then stirred at 30° for 2 hr
  6. temperaturemaintaining the mixture at 30°
  7. stirringThe mixture is stirred 5 hr at 30°
  8. temperaturecooled to 0°
  9. customquenched with sulfuric acid (1 ml)
  10. additionMethanol (89 ml) is added
  11. temperaturethe mixture is heated to 55°
  12. customThe solvent is then removed by reduced pressure until the boiling point
  13. temperatureThe mixture is then cooled to 32°
  14. additionwater (105 ml) is added over 12 min
  15. temperatureThe mixture is further cooled to 0°
  16. filtrationthe the solids are collected by vacuum filtration
  17. washwashed with water

Sources & evidence

ORD record
ord-e5db5e8b040c4bb5a6484c6469072a39
Source dataset
uspto-grants-1990_05
Patent number
US04921638

Reaction notes

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