Methanesulfonic Acid → 9-Dehydroandrostenedione

HRID 1087681Notes

Reaction equation

HRID 1087681 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.CS(O)(=O)=O>O>[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

4

Reactant 2

HCID 6395Methanesulfonic Acid2×HCID 104250179alpha-Hydroxyandrost-4-ene-3,17-dione

Product 1

HCID 2395959-Dehydroandrostenedione

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

9α-Hydroxyandrostenedione (280 mg.; 302 mg. of 92.7% purity) is added to a solution of water (3 ml.) and methanesulfonic acid (1 ml.) and stirred at 22° for 2 hours. Additional methanesulfonic acid (1 ml.) is added and stirred for 6 hours with heating to 68°. The reaction mixture is quenched by addition of water (20 ml.) and benzene (20 ml.). Work-up gives androsta-4,9(11)-diene-3,17-dione, 147 mg. (55.7% chemical yield); m.p. 186°-194°. 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. stirringstirred for 6 hours
  2. temperaturewith heating to 68°
  3. customThe reaction mixture is quenched by addition of water (20 ml.) and benzene (20 ml.)

Sources & evidence

ORD record
ord-ee382e3a1c7d484fbfa170b77629382c
Source dataset
uspto-grants-1990_10
Patent number
USRE033364

Reaction notes

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