Hydrogen Bromide → 5-Bromoquinoline

HRID 1814298Notes

Reaction equation

HRID 1814298 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:7]=1[CH:8]=[CH:9][CH:10]=[N:11]2.[OH-].[Na+].[BrH:18]>O.[Cu]Br>[Br:18][C:6]1[CH:15]=[CH:14][CH:13]=[C:12]2[C:7]=1[CH:8]=[CH:9][CH:10]=[N:11]2

Participants

7

Reactant 4

HCID 260Hydrogen Bromide2×HCID 119115-Aminoquinoline2×HCID 14798Sodium HydroxideHCID 23668193Sodium Nitrite2×

Product 1

HCID 8173215-BromoquinolineYield 80%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 962WaterSolvent2×

Conditions

Temperature
75 °C

Procedure

Sodium nitrite (2.5 g, 41.8 mmol) was dissolved in 15 mL water. Copper (I) bromide (6.0 g, 41.8 mmol) was dissolved in 38 mL of 48% HBr and heated to 75° C. The 5-aminoquinoline (5.0 g, 34.7 mmol) was suspended in 15 mL water and 18 mL 48% HBr and cooled to 0° C. The sodium nitrite solution was added to the 5-aminoquinoline solution at 0° C. The resulting diazonium solution was added slowly to the warmed CuBr solution. The reaction mixture was stirred at room temperature for 2 hr. The reaction mixture was basified with sodium hydroxide, then filtered through celite. The solid was washed with methylene chloride, and the aqueous material was extracted with methylene chloride. The organic layers were combined, dried with Na2SO4, and concentrated in vacuo. The crude product was chromatographed with 2:1 hexane/ethyl acetate to yield 5.7 g (80%) of 5-bromo-quinoline as a yellow oil. MS (APCI) m/z 208.0 (M+1).

Workup

  1. filtrationfiltered through celite
  2. washThe solid was washed with methylene chloride
  3. extractionthe aqueous material was extracted with methylene chloride
  4. dry with materialdried with Na2SO4
  5. concentrationconcentrated in vacuo
  6. customThe crude product was chromatographed with 2:1 hexane/ethyl acetate

Sources & evidence

ORD record
ord-fb9aa80d0c174c348c6bb337571c5edf
Source dataset
uspto-grants-2005_04
Patent number
US06875765B2

Reaction notes

Loading…