Quinoline → 3-Bromo-2-chloro-5-nitropyridine

HRID 2054165Notes

Reaction equation

HRID 2054165 reaction equation
[Br:1][C:2]1[C:3](O)=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.N1C2C(=CC=CC=2)C=CC=1.O=P(Cl)(Cl)[Cl:24]>O>[Br:1][C:2]1[C:3]([Cl:24])=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

5

Reactant 3

HCID 7047QuinolineHCID 24813Phosphorus oxychlorideHCID 178526832HCID 178526832, compound

Product 1

HCID 2308893-Bromo-2-chloro-5-nitropyridineYield 82.7%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

To a cooled (0-5° C.) mixture of 3-bromo-2-hydroxy-5-nitropyridine (47.0 g, 0.214 mol) and quinoline (13.7 g, 0.107 mol) was added POCl3 (26.0 mL, 0.278 mol) dropwise over ˜10 min (the mixture was difficult to stir initially but became less viscous as the reaction progressed and the mixture warmed). After stirring at 120° C. for 3.5 h, the mixture was cooled to 100° C. and water (90 mL) was added. The resulting mixture was stirred vigorously while cooling to 0-5° C. The product was collected by filtration, washed with water and dried in vacuo at 45° C. to give 3-bromo-2-chloro-5-nitropyridine (42.0 g, 82% yield). 1H NMR (CD3OD) δ 9.19 (d, J=2.4 Hz, 1H), 8.93 (d, J=2.4 Hz, 1H).

Workup

  1. temperatureTo a cooled
  2. temperaturethe mixture warmed)
  3. stirringAfter stirring at 120° C. for 3.5 h
  4. stirringThe resulting mixture was stirred vigorously
  5. temperaturewhile cooling to 0-5° C
  6. filtrationThe product was collected by filtration
  7. washwashed with water
  8. customdried in vacuo at 45° C.

Sources & evidence

ORD record
ord-e6afeadf47aa44d8ac1cc416346b40ee
Source dataset
uspto-grants-2008_02
Patent number
US07329656B2

Reaction notes

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