4-Nitrophenol → 17beta-Carbomethoxy-6-t-butylcarboxy-6-azaandrost-1,4-dien-3-one

HRID 1077596Notes

Reaction equation

HRID 1077596 reaction equation
[C:1]([C@H:5]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:6]12[CH2:7][C:8]([OH:10])=[O:9])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]1)[N:16]([C:28]([CH3:31])([CH3:30])[CH3:29])[CH2:15]3)([O:3][CH3:4])=[O:2].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C1C([N+]([O-])=O)=CC=C(O)C=1>O1CCOCC1>[C:1]([C@H:5]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:6]12[CH2:7][C:8]([OH:10])=[O:9])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH:20]=[CH:21]1)[N:16]([C:28]([CH3:31])([CH3:30])[CH3:29])[CH2:15]3)([O:3][CH3:4])=[O:2]

Participants

5

Reactant 3

HCID 9804-NitrophenolHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8674903517beta-Carbomethoxy-6-t-butylcarboxy-6-azaandrost-4-en-3-one

Product 1

HCID 8674971017beta-Carbomethoxy-6-t-butylcarboxy-6-azaandrost-1,4-dien-3-one

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A solution of 17β-carbomethoxy-6-t-butylcarboxy-6-azaandrost-4-en-3-one (2.00 g, 4.63 mmol), prepared in Example 3, part E, in dioxane (50 mL) is treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ, 1.37 g, 6.02 mmol) and p-nitrophenol (10 mg). The reaction is heated to reflux for 2 hrs, poured into ice water (150 mL), extracted with ethyl acetate (3×100 mL), extracts washed with saturated aqueous NaHSO3, 2N NaOH, saturated aqueous NaCl, dried over MgSO4, concentrated and chromatographed on silica gel (40% ethyl acetate/hexanes) to give crude 17β-carbomethoxy-6-t-butylcarboxy-6-azaandrost-1,4-dien-3-one as a tan solid of sufficient purity to carry on to the following steps; yield: 1.53 g (76%).

Workup

  1. temperatureThe reaction is heated
  2. temperatureto reflux for 2 hrs
  3. extractionextracted with ethyl acetate (3×100 mL)
  4. washextracts washed with saturated aqueous NaHSO3, 2N NaOH, saturated aqueous NaCl
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customchromatographed on silica gel (40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-a4b75032ad564863abf9719715a164fc
Source dataset
uspto-grants-1996_08
Patent number
US05543406

Reaction notes

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