Acetic Acid → 17beta-Cyano-17alpha-hydroxy-16beta-methylandrosta-1,4,9(11)-trien-3-one

HRID 1650070Notes

Reaction equation

HRID 1650070 reaction equation
[CH3:1][C@H:2]1[CH2:7][C@H:6]2[C@H:8]3[C:18](=[CH:19][CH2:20][C@:4]2([CH3:5])[C:3]1=[O:22])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:21])[CH:14]=[CH:15]1)[CH2:10][CH2:9]3.[C-:23]#[N:24].[K+].C(O)(=O)C.CC(C)=O.C(Cl)Cl>CO>[C:23]([C@@:3]1([OH:22])[C@@H:2]([CH3:1])[CH2:7][C@H:6]2[C@H:8]3[C:18](=[CH:19][CH2:20][C@:4]12[CH3:5])[C@:16]1([CH3:17])[C:11](=[CH:12][C:13](=[O:21])[CH:14]=[CH:15]1)[CH2:10][CH2:9]3)#[N:24]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 9032Potassium CyanideHCID 1351855816beta-Methylandrosta-1,4,9(11)-triene-3,17-dioneHCID 21584124Propan-2-one--dichloromethane (1/1)

Product 1

HCID 1469759117beta-Cyano-17alpha-hydroxy-16beta-methylandrosta-1,4,9(11)-trien-3-one

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

16β-Methylandrosta-1,4,9(11)-triene-3,17-dione (U.S. Pat. No. 3,010,958, 12.0 g) and potassium cyanide (7.909 g) are suspended in methanol (24 ml). The resulting slurry is then treated with glacial acetic acid (3.5 ml) and allowed to stir in a tightly stoppered flask at 20°-25° for 72 hr. TLC (acetone/methylene chloride, 4/96). The reaction mixture is then cooled to 0° and quenched with glacial acetic acid (4.2 ml). The solids are then collected by filtration, triturated with methanol/water (1/1, 3×10 ml) and dried by heating (60°) under reduced pressure (60 mm) to obtain the title compound, m.p. 241°-247.5°; NMR (CD2Cl2) 1.32, 1.42, 5.58, 6.08, 6.30 and 7.25 δ.

Workup

  1. temperatureThe reaction mixture is then cooled to 0°
  2. customquenched with glacial acetic acid (4.2 ml)
  3. filtrationThe solids are then collected by filtration
  4. customtriturated with methanol/water (1/1, 3×10 ml)
  5. customdried
  6. temperatureby heating (60°) under reduced pressure (60 mm)

Sources & evidence

ORD record
ord-a21e47c3d1b74ddc976a4cb045c17666
Source dataset
uspto-grants-1990_05
Patent number
US04921638

Reaction notes

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