Azobisisobutyronitrile → 4'-bromomethyl-N-(isobutoxycarbonyl)-N-(3-methoxy-5-methylpyrazin-2-yl)-2-biphenylsulphonamide

HRID 1378348Notes

Reaction equation

HRID 1378348 reaction equation
N(C(C)(C)C#N)=NC(C)(C)C#N.[Br:13]N1C(=O)CCC1=O.[CH2:21]([O:25][C:26]([N:28]([C:45]1[C:50]([O:51][CH3:52])=[N:49][C:48]([CH3:53])=[CH:47][N:46]=1)[S:29]([C:32]1[C:33]([C:38]2[CH:43]=[CH:42][C:41]([CH3:44])=[CH:40][CH:39]=2)=[CH:34][CH:35]=[CH:36][CH:37]=1)(=[O:31])=[O:30])=[O:27])[CH:22]([CH3:24])[CH3:23]>C(Cl)(Cl)(Cl)Cl>[Br:13][CH2:44][C:41]1[CH:42]=[CH:43][C:38]([C:33]2[C:32]([S:29]([N:28]([C:26]([O:25][CH2:21][CH:22]([CH3:23])[CH3:24])=[O:27])[C:45]3[C:50]([O:51][CH3:52])=[N:49][C:48]([CH3:53])=[CH:47][N:46]=3)(=[O:31])=[O:30])=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:39][CH:40]=1

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 18704823N-(isobutoxycarbonyl)-N-(3-methoxy-5-methyl-2-pyrazinyl)-4'-methyl-2-biphenylsulphonamide

Product 1

HCID 229112874'-bromomethyl-N-(isobutoxycarbonyl)-N-(3-methoxy-5-methylpyrazin-2-yl)-2-biphenylsulphonamideYield 70.9%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

Azobis(isobutyronitrile) (150 mg) and N-bromosuccinimide (1.68 g) were added to a solution of N-(isobutoxycarbonyl)- N-(3-methoxy-5-methylpyrazin-2-yl)-4'-methyl-2-biphenylsulphonamide (4.44 g) in carbon tetrachloride (150 ml). The mixture was heated under reflux for 4 hours and then allowed to cool and filtered. The filtrate was concentrated by evaporation and the residue was purified by flash chromatography on silica (150 g), eluting with 20% ethyl acetate in isohexane. Fractions containing the product were combined and evaporated to give 4'-bromomethyl- N-(isobutoxycarbonyl)- N-(3-methoxy-5-methylpyrazin-2-yl)-2-biphenylsulphonamide (3.67 g); 1H NMR (d6 -DMSO): 0.6 (s, 6H), 1.6-1.7 (m, 1H), 3.8 (d, 2H), 3.95 (s, 3H), 4.8 (s, 2H), 7.3-7.5 (m, 5H), 7.7-7.8 (m, 2H), 8.15 (s, 1H), 8.45-8.55 (m, 1H); mass spectrum (+ve FAB, methanolBA): 548 (M+H)+.

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux for 4 hours
  3. temperatureto cool
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated by evaporation
  6. customthe residue was purified by flash chromatography on silica (150 g)
  7. washeluting with 20% ethyl acetate in isohexane
  8. additionFractions containing the product
  9. customevaporated

Sources & evidence

ORD record
ord-e78bae5c82704592ac908361c551867a
Source dataset
uspto-grants-1997_09
Patent number
US05668137

Reaction notes

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