Propyne → HCID 67781084, compound

HRID 274302Notes

Reaction equation

HRID 274302 reaction equation
[CH:1]#[C:2][CH3:3].[CH2:4]([Li])[CH2:5][CH2:6]C.C([O:12][C@@H:13]1[C@H:18]2[C@H:19]3[C@H:29]([CH2:30][CH2:31][C@:16]2([CH3:17])[C:15](=O)[CH2:14]1)[C@:27]1([CH3:28])[C:22]([CH:23]=C(OC)CC1)=[CH:21][CH2:20]3)(=O)C.[Cl-].[NH4+].[O:37]1CCCC1>C(OCC)(=O)C>[OH:37][C@@:19]1([C:4]#[C:5][CH3:6])[CH:20]=[CH:21][C@H:22]2[C@H:23]3[C@H:31]([CH2:30][CH2:29][C@:27]12[CH3:28])[C@:16]1([CH3:17])[C:3](=[CH:18][C:13](=[O:12])[CH2:14][CH2:15]1)[CH2:2][CH2:1]3

Participants

7

Reactant 5

HCID 6335PropyneHCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 54571005(15alpha)-15-(Acetyloxy)-3-methoxyandrosta-3,5-dien-17-oneHCID 178418339Butyllithium

Product 1

HCID 67781084HCID 67781084, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

At 0° C., propyne is introduced for 30 minutes into 150 ml of butyllithium solution (1.6 molar in hexane) in 400 ml of tetrahydrofuran. Then 15 g of 15α-acetoxy-3-methoxyandrosta-3,5-dien-17-one in 300 ml of tetrahydrofuran is added dropwise thereto, the mixture is allowed to react for 1 hour and combined with saturated ammonium chloride solution. The mixture is diluted with ethyl acetate, washed with water, dried, and concentrated under vacuum. The crude product is combined dropwise with 10 ml of concentrated hydrochloric acid in a mixture of 300 ml of methanol and 20 ml of water at room temperature. After 1 hour, the reaction mixture is introduced into ice/water, the precipitated product is suctioned off, washed with water, dissolved in ethyl acetate, dried, and concentrated under vacuum. After chromatography of the crude product on silica gel with a hexane-ethyl acetate gradient, 6.3 g of 17β-hydroxy-17α-propyn-1-ylandrosta-4,15-dien-3-one is obtained as a foam.

Workup

  1. customto react for 1 hour
  2. washwashed with water
  3. customdried
  4. concentrationconcentrated under vacuum
  5. additionThe crude product is combined dropwise with 10 ml of concentrated hydrochloric acid in a mixture of 300 ml of methanol and 20 ml of water at room temperature
  6. additionthe reaction mixture is introduced into ice/water
  7. washwashed with water
  8. dissolutiondissolved in ethyl acetate
  9. customdried
  10. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-75c8f2d45dc24064b6f045aa62b12d42
Source dataset
uspto-grants-1995_02
Patent number
US05389624

Reaction notes

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