Hydrogen Bromide → HCID 44891120, compound

HRID 1028987Notes

Reaction equation

HRID 1028987 reaction equation
Cl.[Br:2][C:3]1[CH:9]=[C:8]([F:10])[CH:7]=[C:6]([CH3:11])[C:4]=1N.N([O-])=O.[Na+].CCO.[BrH:19]>[Cu]Br>[Br:2][C:3]1[CH:9]=[C:8]([F:10])[CH:7]=[C:6]([CH3:11])[C:4]=1[Br:19]

Participants

6

Reactant 4

HCID 260Hydrogen Bromide2×HCID 702EthanolHCID 23668193Sodium NitriteHCID 86676840HCID 86676840, compound

Product 1

HCID 44891120HCID 44891120, compound

Reagents, catalysts & solvents 1

HCID 24593copper(I) bromideCatalyst

Procedure

A solution of 2-bromo-4-fluoro-6-methylaniline HCl (5.0 g, 17.6 mmol) in 25% aq. HBr (38.1 mL, 175 mmol) was cooled to 0° C. and an aq. solution of sodium nitrite (0.59 mL, 18.4 mmol) added, followed by a small amount of EtOH to aid solubility. The reaction was stirred at this temperature for 25 min before transferring by pipette to a solution of copper(I) bromide (2.64 g, 18.4 mmol) in 25% aq. HBr (20 ml) at 70° C. The reaction was stirred at this temperature for 3 h. The reaction was quenched with NaHCO3 and the aqueous layer was extracted with EtOAc. The organic layer was then washed with water and brine (3× ea.), dried over Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatography (0-10% Hexene/EtOAC) to yield 1,2-dibromo-5-fluoro-3-methylbenzene as a clear oil.

Workup

  1. stirringThe reaction was stirred at this temperature for 3 h
  2. customThe reaction was quenched with NaHCO3
  3. extractionthe aqueous layer was extracted with EtOAc
  4. washThe organic layer was then washed with water and brine (3× ea.)
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified by column chromatography (0-10% Hexene/EtOAC)

Sources & evidence

ORD record
ord-0be93410a5214c76a3a172bac8ea4e1a
Source dataset
uspto-grants-2014_05
Patent number
US08735384B2

Reaction notes

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