4-Aminophenol → 4-(3-Bromopyridin-2-yloxy)benzenamine

HRID 410218Notes

Reaction equation

HRID 410218 reaction equation
[Br:1][C:2]1[C:3](Cl)=[N:4][CH:5]=[CH:6][CH:7]=1.[NH2:9][C:10]1[CH:15]=[CH:14][C:13]([OH:16])=[CH:12][CH:11]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>CS(C)=O.O>[Br:1][C:2]1[C:3]([O:16][C:13]2[CH:14]=[CH:15][C:10]([NH2:9])=[CH:11][CH:12]=2)=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 4034-AminophenolHCID 10796Cesium carbonateHCID 6933243-Bromo-2-chloropyridine

Product 1

HCID 577562564-(3-Bromopyridin-2-yloxy)benzenamine

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 3-bromo-2-chloropyridine (75.50 g, 392.3 mmol, Aldrich), 4-aminophenol (51.46 g, 471.6 mmol, TCI America) and cesium carbonate (256.80 g, 788.2 mmol, Strem) in DMSO (400 mL) in a 1 L flask and heated at 80° C. overnight. The reaction was cooled (0° C.) and diluted with water. After stirring for 30 min the mixture was filtered and the solid was partitioned between 50% EtOAc/hexane (1 L) and water (300 mL). The organic layer was washed with water (3×300 mL) and with brine (1×200 mL) then dried over Na2SO4. Filtration and concentration in vacuo gave a brown amorphous solid. MS (ESI, pos. ion) m/z: 264.9, 266.9 (M+1).

Workup

  1. temperatureThe reaction was cooled (0° C.)
  2. filtrationwas filtered
  3. customthe solid was partitioned between 50% EtOAc/hexane (1 L) and water (300 mL)
  4. washThe organic layer was washed with water (3×300 mL) and with brine (1×200 mL)
  5. dry with materialthen dried over Na2SO4
  6. filtrationFiltration and concentration in vacuo
  7. customgave a brown amorphous solid

Sources & evidence

ORD record
ord-931cc2a9cf424d98a6364ade57c29cac
Source dataset
uspto-grants-2014_06
Patent number
US08759532B2

Reaction notes

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