Bromine → (4-Bromo-2-methylphenyl)(methyl)sulfane

HRID 891325Notes

Reaction equation

HRID 891325 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[S:8][CH3:9].[Br:10]Br>C(Cl)Cl.[Fe]>[Br:10][C:6]1[CH:5]=[CH:4][C:3]([S:8][CH3:9])=[C:2]([CH3:1])[CH:7]=1

Participants

5

Reactant 2

HCID 24408BromineHCID 2597431-Methyl-2-(methylsulfanyl)benzene

Product 1

HCID 21934395(4-Bromo-2-methylphenyl)(methyl)sulfaneYield 96.3%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 6344DichloromethaneSolvent

Procedure

To a 0° C. solution of 2-methylthioanisole (0.50 g, 3.57 mmol) in methylene chloride (40 mL) was added powdered Fe (20 mg, 0.36 mmol) followed by dropwise addition of bromine (0.58 g, 3.54 mmol). After 30 minutes, the starting material had been consumed (thin layer chromatography, hexanes). The excess bromine was quenched by adding a solution of NaHSO3 and stirring for several minutes. The methylene chloride layer was separated, and the aqueous phase extracted with additional methylene chloride. The combined methylene chloride solution was dried over MgSO4, filtered, and concentrated in vacuo. The resultant oil was chromatographed (flash silica gel, ethyl acetate/hexanes 1:49) to provide the product (yield: 0.74 g, 96%). 1H NMR (300 MHz, CDCl3) δ 2.30 (s, 3H), 2.45 (s, 3H), 7.00 (d, J=8.4 Hz, 1H), 7.27-7.33 (m, 2H).

Workup

  1. customthe starting material had been consumed (thin layer chromatography, hexanes)
  2. customThe excess bromine was quenched
  3. additionby adding a solution of NaHSO3
  4. customThe methylene chloride layer was separated
  5. extractionthe aqueous phase extracted with additional methylene chloride
  6. dry with materialThe combined methylene chloride solution was dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe resultant oil was chromatographed (flash silica gel, ethyl acetate/hexanes 1:49)

Sources & evidence

ORD record
ord-4d1cd68c075a44509f4e881c240cbacb
Source dataset
uspto-grants-2006_02
Patent number
US07001895B2

Reaction notes

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