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

HRID 1288752Notes

Reaction equation

HRID 1288752 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-378511f6428c4d94be9fb85a4fa61969
Source dataset
uspto-grants-1998_05
Patent number
US05747424

Reaction notes

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