Water → 17beta-(1-Oxo-3-methylbutyl)-6-t-butylcarboxy-6-azaandrost-4-en-3-one

HRID 1077594Notes

Reaction equation

HRID 1077594 reaction equation
[OH:1][CH:2]([C@H:7]1[CH2:15][CH2:14][C@H:13]2[C@H:16]3[C@H:26]([CH2:27][CH2:28][C@:8]12[CH2:9][C:10]([OH:12])=[O:11])[C@:24]1([CH3:25])[C:19](=[CH:20][C:21](=[O:29])[CH2:22][CH2:23]1)[N:18]([C:30]([CH3:33])([CH3:32])[CH3:31])[CH2:17]3)[CH2:3][CH:4]([CH3:6])[CH3:5].[Cr](O[Cr]([O-])(=O)=O)([O-])(=O)=O.[NH+]1C=CC=CC=1.[NH+]1C=CC=CC=1.O>CN(C=O)C>[O:1]=[C:2]([C@H:7]1[CH2:15][CH2:14][C@H:13]2[C@H:16]3[C@H:26]([CH2:27][CH2:28][C@:8]12[CH2:9][C:10]([OH:12])=[O:11])[C@:24]1([CH3:25])[C:19](=[CH:20][C:21](=[O:29])[CH2:22][CH2:23]1)[N:18]([C:30]([CH3:31])([CH3:32])[CH3:33])[CH2:17]3)[CH2:3][CH:4]([CH3:5])[CH3:6]

Participants

5

Reactant 3

HCID 962WaterHCID 2724130Cornforth reagentHCID 8674970817beta-(1-Hydroxy-3-methylbutyl)-6-t-butylcarboxy-6-azaandrost-4-en-3-one

Product 1

HCID 8674970917beta-(1-Oxo-3-methylbutyl)-6-t-butylcarboxy-6-azaandrost-4-en-3-one

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 17β-(1-hydroxy-3-methylbutyl)-6-t-butylcarboxy-6-azaandrost-4-en-3-one (160 mg, 0.349 mmol) prepared in part C above, in DMF (10 mL) is treated with pyridinium dichromate (656 mg, 1.74 mmol) at room temperature. After 10 hrs the reaction is poured into water, extracted with ethyl acetate (2×50 mL), the extracts are dried over MgSO4, concentrated and chromatographed on silica gel (40% ethyl acetate/hexanes) to give crude 17β-(1 -oxo-3-methylbutyl)-6-t-butylcarboxy-6-azaandrost-4-en-3-one; yield: 135 mg (85%). A portion of this material (81 mg, 0.18 mmol) is treated with trifluoroacetic acid as described in Example 4 above to give, after recrystallization from diethyl ether/hexanes 17β-(1-oxo-3-methylbutyl)-6-azaandrost-4-en-3-one as a white crystalline solid; yield: 58 mg (92%); m.p. 169°-171° C. Anal. Calcd. for C23H35NO2 ·1/4H2O; C, 76.30; H, 9.88; N, 3.87. Found: C, 76.48; h, 9.93; N, 3.89.

Workup

  1. extractionextracted with ethyl acetate (2×50 mL)
  2. dry with materialthe extracts are dried over MgSO4
  3. concentrationconcentrated
  4. customchromatographed on silica gel (40% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c5d0995725f7414280447a8a872e0983
Source dataset
uspto-grants-1996_08
Patent number
US05543406

Reaction notes

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