Acetylene → HCID 86747115, compound

HRID 2254622Notes

Reaction equation

HRID 2254622 reaction equation
C#C.[CH2:3]([Li])[CH2:4]CC.C(O[C@@H:12]1[C@H:17]2[C@H:18]3[C@H:28]([CH2:29][CH2:30][C@:15]2([CH3:16])[C:14](=[O:33])[CH2:13]1)[C@:26]1([CH3:27])[C:21]([CH:22]=[C:23]([O:31]C)[CH2:24][CH2:25]1)=[CH:20][CH2:19]3)(=O)C.[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[C:3]([C@:14]1([OH:33])[CH:13]=[CH:12][C@H:17]2[C@H:18]3[C@H:28]([CH2:29][CH2:30][C@:15]12[CH3:16])[C@:26]1([CH3:27])[C:21](=[CH:22][C:23](=[O:31])[CH2:24][CH2:25]1)[CH2:20][CH2:19]3)#[CH:4]

Participants

7

Reactant 4

HCID 6326AcetyleneHCID 25517Ammonium ChlorideHCID 54571005(15alpha)-15-(Acetyloxy)-3-methoxyandrosta-3,5-dien-17-oneHCID 178418339Butyllithium

Product 1

HCID 86747115HCID 86747115, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Acetylene is introduced at 0° C. for 45 minutes into 200 ml of butyllithium solution (1.6 molar in hexane) in 600 ml of tetrahydrofuran. Then, 20.0 g of 15α-acetoxy-3-methoxyandrosta-3,5-dien-17-one in 400 ml of tetrahydrofuran is added thereto. After 2 hours, the mixture is gently combined with saturated ammonium chloride solution, diluted with ethyl acetate, washed with water, dried, and concentrated under vacuum. At room temperature, 14 ml of concentrated hydrochloric acid is added dropwise to the crude product in 400 ml of methanol and 50 ml of water. After 1.5 hours, the reaction mixture is stirred into ice/water. The thus-precipitated product is suctioned off, washed with water, dissolved in ethyl acetate, dried, and concentrated under vacuum. The crude product is chromatographed on silica gel with a hexane-ethyl acetate gradient, thus obtaining 9.5 g of 17α-ethynyl-17β-hydroxyandrosta-4,15-diene-3-one, mp 206.4° C. (from acetone/hexane).

Workup

  1. washwashed with water
  2. customdried
  3. concentrationconcentrated under vacuum
  4. additionAt room temperature, 14 ml of concentrated hydrochloric acid is added dropwise to the crude product in 400 ml of methanol and 50 ml of water
  5. waitAfter 1.5 hours
  6. washwashed with water
  7. dissolutiondissolved in ethyl acetate
  8. customdried
  9. concentrationconcentrated under vacuum
  10. customThe crude product is chromatographed on silica gel with a hexane-ethyl acetate gradient

Sources & evidence

ORD record
ord-70147dd731e4422bb19cb85ab011bf00
Source dataset
uspto-grants-1993_08
Patent number
US05236912

Reaction notes

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