Hydrogen Bromide → 2-Bromo-1-chloro-4-(methylsulfonyl)benzene

HRID 1466443Notes

Reaction equation

HRID 1466443 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:6]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:5][C:3]=1N.N([O-])=O.[Na+].[BrH:17]>O.[Cu]Br>[Br:17][C:3]1[CH:5]=[C:6]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:7]=[CH:8][C:2]=1[Cl:1]

Participants

6

Reactant 3

HCID 260Hydrogen BromideHCID 18110852-Chloro-5-methanesulfonylanilineHCID 23668193Sodium Nitrite

Product 1

HCID 592516212-Bromo-1-chloro-4-(methylsulfonyl)benzeneYield 83%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

To a slurry of 2-chloro-5-methanesulfonyl-aniline (4.50 g, 21.9 mmol) in 48% HBr (12 mL) at 0° C. was added dropwise a solution of sodium nitrite (2.28 g, 33 mmol) in H2O (8 mL) at such a rate that the temperature never exceeds 5° C. The resulting yellow mixture was allowed to stir 20 min at 0° C. and then charged with copper(I) bromide (3.3 g, 23 mmol). After 30 min the resulting mixture was extracted with EtOAc (2×100 mL) and the combined extracts were washed successively with satd NH4Cl, 3N HCl and brine, then dried (Na2SO4) and concentrated under reduced pressure. The resulting residue was purified by chromatography (silica, EtOAc/Hex, 0:100 to 50:50) to give the title compound (4.92 g, 83%) as a white solid. GC-MS (EI): 268, 270.

Workup

  1. extractionAfter 30 min the resulting mixture was extracted with EtOAc (2×100 mL)
  2. washthe combined extracts were washed successively with satd NH4Cl, 3N HCl and brine
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated under reduced pressure
  5. customThe resulting residue was purified by chromatography (silica, EtOAc/Hex, 0:100 to 50:50)

Sources & evidence

ORD record
ord-2d2cb1ddd15b4dcfa06a1843a478175a
Source dataset
uspto-grants-2015_04
Patent number
US09000022B2

Reaction notes

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