Methyl iodide → 2-Bromo-4-fluoro-1-(methylsulfonyl)benzene

HRID 1771543Notes

Reaction equation

HRID 1771543 reaction equation
C(=O)([O-])O.[Na+].S([O-])([O-])=O.[Na+].[Na+].[Br:12][C:13]1[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=1[S:20](Cl)(=[O:22])=[O:21].[CH3:24]I>O.O1CCOCC1.CN(C=O)C>[Br:12][C:13]1[CH:18]=[C:17]([F:19])[CH:16]=[CH:15][C:14]=1[S:20]([CH3:24])(=[O:22])=[O:21]

Participants

8

Reactant 4

HCID 6328Methyl iodideHCID 24437Sodium SulfiteHCID 516892Sodium BicarbonateHCID 27782162-Bromo-4-fluorobenzene-1-sulfonyl chloride

Product 1

HCID 532169842-Bromo-4-fluoro-1-(methylsulfonyl)benzeneYield 81.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

Sodium hydrogen carbonate (1.59 g, 18.87 mmol) and sodium sulfite (1.59 g, 12.58 mmol) were heated in water (10 mL) at 70° C. for 5 min. A mixture of 2-bromo-4-fluoro-benzene sulfonyl chloride (1.72 g, 6.29 mmol) in dioxane (15 mL) was added to the base solution and stirred at 70° C. overnight. The solvents were removed in vacuo, DMF (15 mL) and methyl iodide (0.43 mL, 6.85 mmol) were added and reaction mixture stirred at 40° C. overnight. The reaction mixture was concentrated in vacuo, EtOAc (10 ml) added, washed with water (90 ml) and concentrated in vacuo to leave a colourless oil. The resulting oil was purified by flash chromatography (0-10% EtOAc in petroleum ether (40:60) followed by 100% MeOH) to afford 2-bromo-4-fluoro-1-(methylsulfonyl)benzene as an orange oil (1.3 g, 81%).

Workup

  1. additionwas added to the base solution
  2. additionwere added
  3. customreaction mixture
  4. stirringstirred at 40° C. overnight
  5. concentrationThe reaction mixture was concentrated in vacuo, EtOAc (10 ml)
  6. additionadded
  7. washwashed with water (90 ml)
  8. concentrationconcentrated in vacuo
  9. customto leave a colourless oil
  10. customThe resulting oil was purified by flash chromatography (0-10% EtOAc in petroleum ether (40:60) followed by 100% MeOH)

Sources & evidence

ORD record
ord-99397247669746f584778e1855a51eb1
Source dataset
uspto-grants-2016_02
Patent number
US09249129B2

Reaction notes

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