1-Hydroxyethyl radical → 17alpha-Ethinyl-17beta-methoxyandrost-4-en-3-one

HRID 848778

Reaction equation

HRID 848778 reaction equation
[O-][CH2:2]C.[CH3:4][C@@:5]12[C@H:15]3[CH2:16][CH2:17][C@:18]4([CH3:26])[C@:22]([OH:25])([C:23]#[CH:24])[CH2:21][CH2:20][C@H:19]4[C@@H:14]3[CH2:13][CH2:12][C:11]1=[CH:10][C:8](=[O:9])[CH2:7][CH2:6]2>C1C=CC=CC=1>[C:23]([C@:22]1([O:25][CH3:2])[CH2:21][CH2:20][C@H:19]2[C@H:14]3[C@H:15]([CH2:16][CH2:17][C@:18]12[CH3:26])[C@:5]1([CH3:4])[C:11](=[CH:10][C:8](=[O:9])[CH2:7][CH2:6]1)[CH2:12][CH2:13]3)#[CH:24]

Participants

4

Reactant 2

HCID 1194401-Hydroxyethyl radicalHCID 5284557Ethisterone

Product 1

HCID 1283687017alpha-Ethinyl-17beta-methoxyandrost-4-en-3-one

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

Thallous ethoxide (0.8 ml.) is added to ethisterone (17α-ethinyl-17β-hydroxyandrost-4-en-3-one, 3.44 g.) in benzene (50 ml.). After mixing, the benzene is removed with the rotary evaporator and acetonitrile (50 ml.), benzene (40 ml.) and methyl iodide (1.7 ml.) are added. The mixture is refluxed and stirred for 2 hours. Additional methyl iodide (2 ml.) is added and the mixture refluxed another 2 hours. The precipitated thallous iodide is filtered off and the filtrate is concentrated to a residue which is taken up in boiling SSB and filtered thru Celite. After concentration the product is column chromatographed over silica gel eluting with increasing amounts of ethyl acetate in SSB. The appropriate fractions (TLC) are pooled and concentrated to give the title compound (recrystallized from SSB): m.p. 127°-131°; UV (ethanol) λ=240 nm (ε=16,500); MS (m/e) 326 and 311; IR (mull) 3240, 2100, 1670 and 1620 cm-1.

Workup

  1. additionAfter mixing
  2. customthe benzene is removed with the rotary evaporator and acetonitrile (50 ml.), benzene (40 ml.) and methyl iodide (1.7 ml.)
  3. additionare added
  4. temperatureThe mixture is refluxed
  5. additionAdditional methyl iodide (2 ml.) is added
  6. temperaturethe mixture refluxed another 2 hours
  7. customThe precipitated thallous iodide
  8. filtrationis filtered off
  9. concentrationthe filtrate is concentrated to a residue which
  10. filtrationfiltered thru Celite
  11. concentrationAfter concentration the product
  12. customchromatographed over silica gel eluting with increasing amounts of ethyl acetate in SSB
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-6a68a7f5df1e442dbf3b9b127b5ac53b
Source dataset
uspto-grants-1981_10
Patent number
US04297350

Linked notes

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