1,4-Dibromobutane → HCID 54225991, compound

HRID 1463779Notes

Reaction equation

HRID 1463779 reaction equation
[C:1]([NH:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]1)[NH:16][CH2:15]3)=[O:7])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].[Br:30][CH2:31][CH2:32][CH2:33][CH2:34]Br>CN(C)C=O>[C:1]([NH:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17](=[CH:18][C:19](=[O:27])[CH2:20][CH2:21]1)[N:16]([CH2:34][CH2:33][CH2:32][CH2:31][Br:30])[CH2:15]3)=[O:7])([CH3:2])([CH3:3])[CH3:4]

Participants

5

Reactant 3

HCID 80561,4-DibromobutaneHCID 24758Sodium hydrideHCID 9999375HCID 9999375, compound

Product 1

HCID 54225991HCID 54225991, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 17β-N-t-butylcarbamoyl-6-azaandrost-4-en-3-one (373 mg. 1.00 mmol), in dimethylformamide is treated with sodium hydride (50 mg, 60%, 1.25 mmol) at 0° C. for 30 minutes before the addition of 1,4-dibromobutane (0.179 mL, 1.5 mmol). After 30 minutes further the reaction is poured into ice water and extracted with methylene chloride (3×10 mL), dried over Na2SO4, concentrated and filtered through a plug of silica with 1:1 methylene chloride/acetonitrile followed by 10% methanol/methylene chloride. The methanolic fractions are concentrated to give crude 17β-N-t-butylcarbamoyl-6-(4-bromobutyl)-6-azaandrost-4-en-3-one. This material is dissolved in toluene (5 mL) and dimethylformamide (1.5 mL), sodium iodide added and the mixture heated at reflux for 7 hrs. The reaction is cooled, water added, extracted with methylene chloride (3×20 mL), dried over Na2SO4, concentrated and chromatographed (50% ethyl acetate/hexane) to give 17β-N-t-butylcarbamoyl-6-azaandrost-4,6-butano-4-en-3-one as a white solid; yield: 150 mg (35%). Recrystallization from ethyl acetate/hexanes gives an analytical sample as white crystals; m.p. 173°-174° C. Anal. Calcd. for C27H42N2O2.1/4H2O; C, 75.29; H, 9.94; N, 6.50. Found: C, 75.21; H, 10.04; N, 6.20.

Workup

  1. extractionextracted with methylene chloride (3×10 mL)
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated
  4. filtrationfiltered through a plug of silica with 1:1 methylene chloride/acetonitrile
  5. concentrationThe methanolic fractions are concentrated

Sources & evidence

ORD record
ord-c1c9d5daf6d6412a8c8c4fbce1cd02ae
Source dataset
uspto-grants-1994_04
Patent number
US05302589

Reaction notes

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