Water → 9-Dehydroandrostenedione

HRID 1704667Notes

Reaction equation

HRID 1704667 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.ClS(O)(=O)=O.O>C(Cl)Cl>[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 962WaterHCID 24638Chlorosulfonic acidHCID 104250179alpha-Hydroxyandrost-4-ene-3,17-dione

Product 1

HCID 2395959-Dehydroandrostenedione

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

9α-Hydroxyandrostenedione (10.00 g.) is dissolved in methylene chloride (100 ml.) and cooled to 0°-5°. Chlorosulfonic acid (5 ml.) is added dropwise and the mixture stirred for 0.5 hour at 0°-5°. Water (50 ml.) is added dropwise while the temperature rises to 23°. The mixture is stirred for 5 minutes and the phases separated. The organic phase is washed with an aqueous sodium bicarbonate solution (10%, 25 ml.) and water (50 ml.) containing 10 ml. of a saturated sodium chloride solution. Each of the aqueous washes is back extracted with the same methylene chloride (25 ml.) which is then added to the organic phase. The organic phase is concentrated to approximately 50 ml. Heptane (100 ml.) is added and the mixture concentrated to approximately 50 ml. with the temperature reaching a maximum of about 35°. The mixture is cooled to 0°-5°, stirred 0.5 hour, the solids are collected by filtration, washed with a minimum amount of heptane, and dried under vacuum at 55° to give androsta-4,9(11)-diene-3,17-dione, 8.95 g. (89.5% weight yield, 95.0% chemical yield). GC (Example 1) shows 99% androsta-4,9(11)-diene-3,17-dione.

Workup

  1. temperaturecooled to 0°-5°
  2. customrises to 23°
  3. stirringThe mixture is stirred for 5 minutes
  4. customthe phases separated
  5. washThe organic phase is washed with an aqueous sodium bicarbonate solution (10%, 25 ml.) and water (50 ml.)
  6. additioncontaining 10 ml
  7. extractionEach of the aqueous washes is back extracted with the same methylene chloride (25 ml.) which
  8. additionis then added to the organic phase
  9. concentrationThe organic phase is concentrated to approximately 50 ml
  10. additionHeptane (100 ml.) is added
  11. concentrationthe mixture concentrated to approximately 50 ml
  12. customa maximum of about 35°
  13. temperatureThe mixture is cooled to 0°-5°
  14. stirringstirred 0.5 hour
  15. filtrationthe solids are collected by filtration
  16. washwashed with a minimum amount of heptane
  17. customdried under vacuum at 55°

Sources & evidence

ORD record
ord-4a0c3a757cd043d4b383cb543822f33d
Source dataset
uspto-grants-1978_11
Patent number
US04127596

Reaction notes

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