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

HRID 1046658Notes

Reaction equation

HRID 1046658 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-ae2108768099484b810c9229eaa5ecd2
Source dataset
uspto-grants-2013_10
Patent number
US08569352B2

Reaction notes

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