Ammonia → 3-(3,5-Dibromophenoxy)pyridine

HRID 2210058Notes

Reaction equation

HRID 2210058 reaction equation
[H-].[Na+].[OH:3][C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1.[Br:10][C:11]1[CH:16]=[C:15](Br)[CH:14]=[C:13]([Br:18])[CH:12]=1.N1C(C)=CC(C)=CC=1C.[H][H].N>C(OCC)(=O)C.O>[Br:10][C:11]1[CH:16]=[C:15]([CH:14]=[C:13]([Br:18])[CH:12]=1)[O:3][C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1

Participants

9

Reactant 6

HCID 222AmmoniaHCID 79532,4,6-TrimethylpyridineHCID 79713-HydroxypyridineHCID 122791,3,5-TribromobenzeneHCID 24758Sodium hydrideHCID 178418361HCID 178418361, compound

Product 1

HCID 106877623-(3,5-Dibromophenoxy)pyridineYield 34.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

Sodium hydride (3.24 g of a 60% dispersion in mineral oil) was added portionwise to a stirred mixture of 3-hydroxypyridine (15.4 g), 1,3,5-tribromobenzene (76.4 g), cuprous oxide (11.6 g) and collidine (400 ml). When evolution of hydrogen had ceased, the mixture was heated at 200° for 8 hours and then cooled. The cool mixture was diluted with ethyl acetate and water, basified with aqueous ammonia (SG 0.880) and then filtered. The filtered residue was washed with ethyl acetate, then the washings and organic phase of the filtrate combined, washed with saturated brine and dried (MgSO4). The ethyl acetate was evaporated under vacuum, the collidine removed by distillation under vacuum and the residue chromatographed on silica gel using ether:hexane (1:4) as eluent. The earlier fractions gave, after evaporation under vacuum, recovered tribromobenzene (42.5 g). The later fractions were evaporated under vacuum to afford the title compound as an oil (18.55 g); δ (CDCl3): 7.07(2H,s), 7.22-7.26(2H,m), 7.42 (1H,s), 8.42(1H,s), 8.47(1H,d). Found: C,40.49; H,2.17; N,4.19. C11H7Br2NO requires C,40.16; H,2.14; N,4.26%.

Workup

  1. temperaturethe mixture was heated at 200° for 8 hours
  2. temperaturecooled
  3. filtrationfiltered
  4. washThe filtered residue was washed with ethyl acetate
  5. washwashed with saturated brine
  6. dry with materialdried (MgSO4)
  7. customThe ethyl acetate was evaporated under vacuum
  8. customthe collidine removed by distillation under vacuum
  9. customthe residue chromatographed on silica gel
  10. customThe earlier fractions gave
  11. customafter evaporation under vacuum
  12. customrecovered tribromobenzene (42.5 g)
  13. customThe later fractions were evaporated under vacuum

Sources & evidence

ORD record
ord-fe76641c11f34fd38fbfc0335385f539
Source dataset
uspto-grants-1995_10
Patent number
US05457118

Reaction notes

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