Sulfuric Acid → 9-Dehydroandrostenedione

HRID 1087677

Reaction equation

HRID 1087677 reaction equation
O[C@:2]12[CH2:19][CH2:18][C@@:16]3([CH3:17])[C@@H:12]([CH2:13][CH2:14][C:15]3=[O:20])[C@@H:11]1[CH2:10][CH2:9][C:8]1[C@:3]2([CH3:22])[CH2:4][CH2:5][C:6](=[O:21])[CH:7]=1.S(=O)(=O)(O)O.C(OCC)(=O)C>CCCCCC>[CH3:17][C@:16]12[CH2:18][CH:19]=[C:2]3[C@@H:11]([CH2:10][CH2:9][C:8]4[C@:3]3([CH3:22])[CH2:4][CH2:5][C:6](=[O:21])[CH:7]=4)[C@@H:12]1[CH2:13][CH2:14][C:15]2=[O:20]

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 8857Ethyl AcetateHCID 104250179alpha-Hydroxyandrost-4-ene-3,17-dione

Product 1

HCID 2395959-Dehydroandrostenedione

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

9α-Hydroxyandrostenedione (9.07 g.) is added to aqueous sulfuric acid (22.5 ml. of 70%; 3 parts water and 7 parts sulfuric acid). The resulting slurry is stirred at 23°-25° until the reaction is complete as measured by TLC(ethyl acetate:hexane, 60:40). When complete the reaction mixture is cooled (10°) and added dropwise to ice-water (800 ml.) with rapid stirring. The resulting slurry is stirred overnight, filtered and the solids washed with water (500 ml.), sodium bicarbonate solution (10%, 500 ml.) and water (500 ml.). The solids are air-dried to give androsta-4,9(11)-diene-3,17-dione, 8.31 g. (97.4% chemical yield); m.p. 196°201°; [α]D +219° (chloroform); UV (methanol)λmax =240 nm (ε=16,500). GC (Example 1) shows an androsta-4,9(11)-diene-3,17-dione/androsta-4,8-diene-3,17-dione ratio of greater than 99 to 1.

Workup

  1. temperatureWhen complete the reaction mixture is cooled (10°)
  2. stirringThe resulting slurry is stirred overnight
  3. filtrationfiltered
  4. washthe solids washed with water (500 ml.), sodium bicarbonate solution (10%, 500 ml.) and water (500 ml.)
  5. customThe solids are air-dried

Sources & evidence

ORD record
ord-249822e8486f4e26a1dff3d73c904c82
Source dataset
uspto-grants-1990_10
Patent number
USRE033364

Linked notes

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