Hydrogen Bromide → 4-Bromo-1-methyl-2-(methylsulfanyl)benzene

HRID 2256950Notes

Reaction equation

HRID 2256950 reaction equation
N([O-])=O.[Na+].[CH3:5][C:6]1[CH:12]=[CH:11][C:9](N)=[CH:8][C:7]=1[S:13][CH3:14].[BrH:15]>S(=O)(=O)(O)O.C(O)(=O)C.O.[Cu]Br>[Br:15][C:9]1[CH:11]=[CH:12][C:6]([CH3:5])=[C:7]([S:13][CH3:14])[CH:8]=1

Participants

8

Reactant 3

HCID 260Hydrogen BromideHCID 23668193Sodium NitriteHCID 5439611398594-08-2

Product 1

HCID 467393114-Bromo-1-methyl-2-(methylsulfanyl)benzene

Reagents, catalysts & solvents 4

HCID 24593copper(I) bromideCatalystHCID 176Acetic AcidSolventHCID 962WaterSolventHCID 1118Sulfuric AcidSolvent

Procedure

A cooled solution of sodium nitrite (5.8 g) in concentrated sulphuric acid (50 ml) was added dropwise to a stirred solution of 4-methyl-3-methylsulphenylaniline (12.8 g) in glacial acetic acid at 20° C. The resulting suspension was added to a mixture of copper (I) bromide (12 g), aqueous hydrobromic acid (48-50%) and ice. The mixture was stirred at room temperature for 3 hours then diluted with water and extracted with ethyl acetate. The organic layer was washed with water, aqueous sodium hydroxide (2M), dried (anhydrous magnesium sulphate) and filtered. The filtrate was evaporated to dryness. The residue was triturated with hot cyclohexane and filtered. The filtrate was evaporated to dryness to give 4-bromo-2-methylsulphenyltoluene (8.6 g) as a brown oil, NMR (CDCl3): 2.15(s,3H), 2.2(s,3H), 6.5-7.1 (m,3H).

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic layer was washed with water, aqueous sodium hydroxide (2M)
  3. dry with materialdried (anhydrous magnesium sulphate)
  4. filtrationfiltered
  5. customThe filtrate was evaporated to dryness
  6. customThe residue was triturated with hot cyclohexane
  7. filtrationfiltered
  8. customThe filtrate was evaporated to dryness

Sources & evidence

ORD record
ord-08c210a38d0c4757bec1bb82001eb3f8
Source dataset
uspto-grants-1997_08
Patent number
US05656573

Reaction notes

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