3-Bromo-o-toluidine → 2-Methyl-3-(methylthio)benzenamine

HRID 992852Notes

Reaction equation

HRID 992852 reaction equation
[CH3:1][S-:2].[Na+].Br[C:5]1[C:6]([CH3:12])=[C:7]([CH:9]=[CH:10][CH:11]=1)[NH2:8]>CN1CCCC1.[Cu]>[CH3:12][C:6]1[C:5]([S:2][CH3:1])=[CH:11][CH:10]=[CH:9][C:7]=1[NH2:8]

Participants

5

Reactant 2

HCID 1235383-Bromo-o-toluidineHCID 4378561Sodium methanethiolate

Product 1

HCID 184083602-Methyl-3-(methylthio)benzenamine

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 84541-MethylpyrrolidineSolvent

Procedure

At 20° C., 4.3 g (61.81 mmol) of sodium thiomethoxide were added with stirring and ice-cooling to 10 g (53.75 mmol) of 3-bromo-2-methylaniline in 100 ml of N-methylpyrrolidine. After addition of 200 mg of copper powder, the reaction mixture was transferred into an autoclave and stirred at 240° C. for 16 h. The reaction solution was subsequently poured into 300 ml of ice-water and extracted 3× with methyl tert-butyl ether. The organic extracts were washed with water, dried and concentrated. The residue was chromatographed over silica gel using methylene chloride, giving 1.7 g (20.6% of theory) of the title compound as a colorless oil.

Workup

  1. stirringstirred at 240° C. for 16 h
  2. extractionextracted 3× with methyl tert-butyl ether
  3. washThe organic extracts were washed with water
  4. customdried
  5. concentrationconcentrated
  6. customThe residue was chromatographed over silica gel

Sources & evidence

ORD record
ord-f84650b5341e493aa73967b557cc91aa
Source dataset
uspto-grants-2002_10
Patent number
US06472349B1

Reaction notes

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