Sulfuric Acid → (17alpha)-17-Hydroxy-3-oxoandrosta-4,9(11)-diene-17-carbonitrile

HRID 1650076Notes

Reaction equation

HRID 1650076 reaction equation
S(=O)(=O)(O)O.[CH3:6][C@@:7]12[C:15]([OH:18])([C:16]#[N:17])[CH2:14][CH2:13][C@H:12]1[C@@H:11]1[CH2:19][CH2:20][C:21]3[C@@:27]([CH3:28])([C:10]1(O)[CH2:9][CH2:8]2)[CH2:26][CH2:25][C:23](=[O:24])[CH:22]=3>O>[C:16]([C@@:15]1([OH:18])[CH2:14][CH2:13][C@H:12]2[C@H:11]3[C:10](=[CH:9][CH2:8][C@:7]12[CH3:6])[C@:27]1([CH3:28])[C:21](=[CH:22][C:23](=[O:24])[CH2:25][CH2:26]1)[CH2:20][CH2:19]3)#[N:17]

Participants

4

Reactant 2

HCID 1118Sulfuric Acid2×HCID 308277817-Cyano-9,17-dihydroxyandrost-4-ene-3-one

Product 1

HCID 10859900(17alpha)-17-Hydroxy-3-oxoandrosta-4,9(11)-diene-17-carbonitrile

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A mixture of sulfuric acid (37 ml) and water (32.1 ml) is added to 17β-cyano-9α,17α-dihydroxyandrost-4-en-3-one (I, EXAMPLE 87, 13.28 g). The mixture is stirred at 20°-25° for 19 hr, stirred at 30° for 4 hr, then cooled to 10°. Sulfuric acid (11.2 ml) is added, the mixture is stirred at 20°-25° for 45 min, then cooled to 0° and water (55 ml) is added, maintaining the temperature at <5°. The product is collected by vacuum filtration and washed with water (80 ml), aqueous ammonium acetate (1M, 80 ml) and water (80 ml). The solid is dried in an air stream for 24 hr to give the title compound, mp 225°-228°.

Workup

  1. stirringstirred at 30° for 4 hr
  2. temperaturecooled to 10°
  3. stirringthe mixture is stirred at 20°-25° for 45 min
  4. temperaturecooled to 0°
  5. temperaturemaintaining the temperature at <5°
  6. filtrationThe product is collected by vacuum filtration
  7. washwashed with water (80 ml), aqueous ammonium acetate (1M, 80 ml) and water (80 ml)
  8. customThe solid is dried in an air stream for 24 hr

Sources & evidence

ORD record
ord-6f13b0dcdf62411ab88e3609568bd319
Source dataset
uspto-grants-1990_05
Patent number
US04921638

Reaction notes

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