p-Tolyl methyl sulfone → 2-Bromo-4-(methanesulfonyl)-1-methylbenzene

HRID 2357667Notes

Reaction equation

HRID 2357667 reaction equation
[Br:1]Br.[C:3]1([CH3:13])[CH:8]=[CH:7][C:6]([S:9]([CH3:12])(=[O:11])=[O:10])=[CH:5][CH:4]=1.S([O-])([O-])(=O)=S.[Na+].[Na+]>[Fe].C(OCC)(=O)C>[Br:1][C:8]1[CH:7]=[C:6]([S:9]([CH3:12])(=[O:11])=[O:10])[CH:5]=[CH:4][C:3]=1[CH3:13]

Participants

6

Reactant 3

HCID 18521p-Tolyl methyl sulfoneHCID 24408BromineHCID 24477Sodium Thiosulfate

Product 1

HCID 532169872-Bromo-4-(methanesulfonyl)-1-methylbenzeneYield 75.1%

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of iron powder (0.0669 g, 1.20 mmol) in bromine (2.05 mL, 39.9 mmol) at 0° C. was added methyl p-tolyl sulfone (0.340 g, 2.00 mmol). The reaction was warmed up to RT and stirred for 2 h. The mixture was poured into an ice-cold 1 M solution of sodium thiosulfate and ethyl acetate. The layers were separated and the aqueous layer was extracted with ethyl acetate (3×). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated to give 545 mg of crude material. The crude material was purified by column chromatography (3/1 Hex/ethyl acetate to 1/1 ethyl acetate/hexanes) to give 374 mg of 2-bromo-1-methyl-4-(methylsulfonyl)benzene as a white solid. ES+=251.0 (M+H)

Workup

  1. customThe layers were separated
  2. extractionthe aqueous layer was extracted with ethyl acetate (3×)
  3. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customto give 545 mg of crude material
  7. customThe crude material was purified by column chromatography (3/1 Hex/ethyl acetate to 1/1 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-ccfecc2491fa430cb8ec2a37f7d28238
Source dataset
uspto-grants-2010_07
Patent number
US07759337B2

Reaction notes

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