Benzene, 1-methyl-3-(methylthio)- → (4-Bromo-3-methylphenyl)(methyl)sulfane

HRID 748909Notes

Reaction equation

HRID 748909 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([S:8][CH3:9])[CH:3]=1.[Br:10]Br>ClCCl.[Fe]>[Br:10][C:7]1[CH:6]=[CH:5][C:4]([S:8][CH3:9])=[CH:3][C:2]=1[CH3:1]

Participants

5

Reactant 2

HCID 21005Benzene, 1-methyl-3-(methylthio)-HCID 24408Bromine

Product 1

HCID 26370189(4-Bromo-3-methylphenyl)(methyl)sulfaneYield 53%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
3 °C

Procedure

Combine iron (25 mg, 0.45 mmol) and 1-methyl-3-methylsulfanyl-benzene (204 mg, 1.47 mmol) in dichloromethane (DCM, 2 mL). Cool the slurry to 3° C. and add Br2 (74 μL, 1.44 mmol) over 5 minutes. Stir at 3° C. for 10 minutes and remove the external cooling bath. Stir at room temperature for 4 hours, then quench with 10% aqueous Na2S2O3 solution. Dilute the reaction with dichloromethane (10 mL) and separate. Wash the organic layer with brine, concentrate and chromatograph with dichloromethane in hexanes (0 to 5%) to give 125 mg of 1-bromo-2-methyl-4-methylsulfanyl-benzene (53%).

Workup

  1. customremove the external cooling bath
  2. stirringStir at room temperature for 4 hours
  3. customquench with 10% aqueous Na2S2O3 solution
  4. additionDilute
  5. customthe reaction with dichloromethane (10 mL)
  6. customseparate
  7. washWash the organic layer with brine
  8. concentrationconcentrate

Sources & evidence

ORD record
ord-88a69afcb5f440338e7b98f27378330f
Source dataset
uspto-grants-2008_07
Patent number
US07399867B2

Reaction notes

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