Azobisisobutyronitrile → HCID 86631888, compound

HRID 910237Notes

Reaction equation

HRID 910237 reaction equation
BrN1C(=[O:7])CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N.[Br:21][C:22]1[CH:27]=[C:26]([CH3:28])[CH:25]=[CH:24][C:23]=1[C:29]1[O:33][CH:32]=[N:31][CH:30]=1>C(Cl)(Cl)(Cl)Cl>[Br:21][C:22]1[CH:27]=[C:26]([CH:25]=[CH:24][C:23]=1[C:29]1[O:33][CH:32]=[N:31][CH:30]=1)[CH:28]=[O:7]

Participants

5

Reactant 3

HCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 67403933HCID 67403933, compound

Product 1

HCID 86631888HCID 86631888, compoundYield 10.9%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

N-Bromosuccinimide (2.36 g) and 2,2′-azobis(2-methylpropionitrile) (164 mg) were added to a solution (100 mL) of 5-(2-bromo-4-methylphenyl)-1,3-oxazole (2.6 g) in carbon tetrachloride, and the mixture was refluxed under heating for 2.5 hours. Insoluble matter was removed through filtration, followed by purification, to thereby yield 5-[2-bromo-4-(bromomethyl)phenyl]-1,3-oxazole (3.2 g). Acetic acid (190 mg) and sodium hydrogencarbonate (336 mg) were added to a solution (50 mL) of the thus-obtained 5-[2-bromo-4-(bromomethyl)phenyl]-1,3-oxazole (500 mg) in anhydrous N,N-dimethylformamide, and the mixture was stirred at room temperature for 23 hours. The solvent was evaporated, and the residue was purified, to thereby yield 3-bromo-4-(1,3-oxazol-5-yl)benzyl acetate (300 mg). This procedure was repeated. 2N Aqueous sodium hydroxide solution (5 mL) was added to a solution (50 mL) of the thus-obtained 3-bromo-4-(1,3-oxazol-5-yl)benzyl acetate (490 mg) in methanol, and the mixture was stirred at room temperature for 30 minutes. The solvent was evaporated, and the residue was purified, to thereby yield [3-bromo-4-(1,3-oxazol-5-yl)phenyl]methanol (350 mg). Manganese dioxide (672 mg) was added to a solution (50 mL) of the thus-obtained [3-bromo-4-(1,3-oxazol-5-yl)phenyl]methanol (350 mg) in chloroform, and the mixture was refluxed under heating for 20 hours. Insoluble matter was removed through filtration by use of Celite, and the filtrate was concentrated under reduced pressure. The residue was purified through silica gel column chromatography (dichloromethane), followed by concentration, to thereby yield the title compound (300 mg).

Workup

  1. temperaturethe mixture was refluxed
  2. temperatureunder heating for 2.5 hours
  3. customInsoluble matter was removed through filtration
  4. customfollowed by purification
  5. additionAcetic acid (190 mg) and sodium hydrogencarbonate (336 mg) were added to a solution (50 mL) of the thus-obtained 5-[2-bromo-4-(bromomethyl)phenyl]-1,3-oxazole (500 mg) in anhydrous N,N-dimethylformamide
  6. customThe solvent was evaporated
  7. customthe residue was purified
  8. addition2N Aqueous sodium hydroxide solution (5 mL) was added to a solution (50 mL) of the thus-obtained 3-bromo-4-(1,3-oxazol-5-yl)benzyl acetate (490 mg) in methanol
  9. stirringthe mixture was stirred at room temperature for 30 minutes
  10. customThe solvent was evaporated
  11. customthe residue was purified
  12. additionManganese dioxide (672 mg) was added to a solution (50 mL) of the thus-obtained [3-bromo-4-(1,3-oxazol-5-yl)phenyl]methanol (350 mg) in chloroform
  13. temperaturethe mixture was refluxed
  14. temperatureunder heating for 20 hours
  15. customInsoluble matter was removed through filtration by use of Celite
  16. concentrationthe filtrate was concentrated under reduced pressure
  17. customThe residue was purified through silica gel column chromatography (dichloromethane)
  18. concentrationfollowed by concentration

Sources & evidence

ORD record
ord-465a4ffa8f1d4828a4a2ea239503e2d8
Source dataset
uspto-grants-2011_09
Patent number
US08022075B2

Reaction notes

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