Azobisisobutyronitrile → HCID 86589971, compound

HRID 1792224Notes

Reaction equation

HRID 1792224 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH2:15][C@@H:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH2:19][C@@H:20]2[CH2:28][O:29][CH2:30][CH2:31][C:32]([N:34]([CH3:36])[CH3:35])=[O:33])[CH2:12][C@@H:11]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:40])[CH3:39])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].Br[N:46]1[C:50](=[O:51])CC[C:47]1=[O:52].[N:53](C(C)(C)C#N)=[N:54]C(C)(C)C#N.CCCCCC>O1CCCC1>[C:16]1([N:46]2[C:50](=[O:51])[N:54]=[N:53][C:47]2=[O:52])[CH:17]=[CH:21][CH:23]=[CH:24][CH:25]=1.[Si:1]([O:8][C@@H:9]1[C@@:26]2([CH3:27])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:25]2[CH2:24][CH2:23][C@@:21]2([CH3:22])[C@H:17]3[CH2:18][CH2:19][C@@H:20]2[CH2:28][O:29][CH2:30][CH2:31][C:32]([N:34]([CH3:35])[CH3:36])=[O:33])[CH2:12][C@@H:11]([O:37][Si:38]([C:41]([CH3:44])([CH3:43])[CH3:42])([CH3:39])[CH3:40])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 6547AzobisisobutyronitrileHCID 8058HexaneHCID 67184N-bromobutanimideHCID 69630616HCID 69630616, compound

Product 1

HCID 86589971HCID 86589971, compoundYield 140.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To 1α,3β-bis(tert-butyldimethylsilyloxy)-17β-(N,N-dimethylaminocarbonylethoxymethyl)androst-5-ene (15 g), were added N-bromosuccinimide (5.36 g), 2,2′-azobis isobutyronitrile (1.06 g), hexane (120 ml) and tetrahydrofuran (30 ml), followed by reflux under heating for 15 min. After cooling to room temperature, the mixture was filtered to remove insoluble material and the filtrate was concentrated under reduced pressure. To the resultant, were added toluene (50 ml) and γ-collidine (9.8 ml), followed by reaction under reflux for 2 hours. After cooling to room temperature, the reaction mixture was filtered and the filtrate was washed with 0.5M hydrochloric acid, a saturated aqueous sodium bicarbonate solution and then saturated brine. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure. To the thus obtained residue, were added dichloromethane (70 ml) and 4-phenyl-1,2,4-triazoline-3,5-dione, followed by reaction at room temperature. The reaction mixture was washed with water, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to remove the solvent. The thus obtained residue was purified by column chromatography (hexane:ethyl acetate=1:2) to give the titled compound (7.43 g).

Workup

  1. temperatureby reflux
  2. temperatureunder heating for 15 min
  3. filtrationthe mixture was filtered
  4. customto remove insoluble material
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. additionTo the resultant, were added toluene (50 ml) and γ-collidine (9.8 ml)
  7. customfollowed by reaction
  8. temperatureunder reflux for 2 hours
  9. temperatureAfter cooling to room temperature
  10. filtrationthe reaction mixture was filtered
  11. washthe filtrate was washed with 0.5M hydrochloric acid
  12. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  13. concentrationconcentrated under reduced pressure
  14. additionTo the thus obtained residue, were added dichloromethane (70 ml) and 4-phenyl-1,2,4-triazoline-3,5-dione
  15. customfollowed by reaction at room temperature
  16. washThe reaction mixture was washed with water
  17. dry with materialdried over anhydrous magnesium sulfate
  18. customevaporated under reduced pressure
  19. customto remove the solvent
  20. customThe thus obtained residue was purified by column chromatography (hexane:ethyl acetate=1:2)

Sources & evidence

ORD record
ord-679f47ec92954ed5999bb1baa4b6b5fd
Source dataset
uspto-grants-2006_07
Patent number
US07074777B2

Reaction notes

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