Pyridine → 3-Bromoquinoline-6-carboxylic acid

HRID 589157Notes

Reaction equation

HRID 589157 reaction equation
[N:1]1[C:10]2[C:5](=[CH:6][C:7]([C:11]([OH:13])=[O:12])=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[Br:14]Br.N1C=CC=CC=1.[OH-].[Na+]>C(Cl)(Cl)(Cl)Cl>[Br:14][C:3]1[CH:2]=[N:1][C:10]2[C:5]([CH:4]=1)=[CH:6][C:7]([C:11]([OH:13])=[O:12])=[CH:8][CH:9]=2

Participants

6

Reactant 4

HCID 1049PyridineHCID 14798Sodium HydroxideHCID 24408BromineHCID 825716-Quinolinecarboxylic acid

Product 1

HCID 178503473-Bromoquinoline-6-carboxylic acidYield 83.3%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent2×

Procedure

To a suspension of quinoline-6-carboxylic acid (2.77 g, 16.0 mmol) in CCl4 (20 ml) in a flask wrapped with Al foil was added bromine (987 uL, 19.2 mmol) dropwise. The resulting mixture was stirred at rt for 30 min, then heated under reflux for 30 min. A solution of pyridine (1.55 mL, 19.2 mmol) in CCl4 (4 mL) was added dropwise at refluxing temperature. Then the reaction mixture was heated under reflux for 4 h. The reaction mixture was treated with 3 N NaOH until all the precipitates were dissolved. The aqueous layer was separated and washed with DCM once more, then acidified with 3 N HCl. The resulting orange precipitates were filtered, and washed with H2O, and a small amount of MeOH to afford the titled compound as an off-white solid (3.36 g).

Workup

  1. temperatureheated
  2. temperatureunder reflux for 30 min
  3. temperatureat refluxing temperature
  4. temperatureThen the reaction mixture was heated
  5. temperatureunder reflux for 4 h
  6. dissolutionwere dissolved
  7. customThe aqueous layer was separated
  8. washwashed with DCM once more
  9. customThe resulting orange precipitates
  10. filtrationwere filtered
  11. washwashed with H2O

Sources & evidence

ORD record
ord-999c2010b36f41bf82ac72382886f657
Source dataset
uspto-grants-2016_01
Patent number
US09227971B2

Reaction notes

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