2-Bromo-1-fluoro-4-nitrobenzene → 2-Bromo-1-methylsulfanyl-4-nitrobenzene

HRID 38203

Reaction equation

HRID 38203 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1F.[CH3:12][S-:13].[Na+]>CN(C=O)C>[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-:10])=[O:9])[CH:5]=[CH:4][C:3]=1[S:13][CH3:12]

Participants

4

Reactant 2

HCID 696992-Bromo-1-fluoro-4-nitrobenzeneHCID 4378561Sodium methanethiolate2×

Product 1

HCID 595508422-Bromo-1-methylsulfanyl-4-nitrobenzene

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 25.7 g (120 mmol) 2-bromo-1-fluoro-4-nitrobenzene in 154 ml DMF is treated with 10.6 g (150 mmol) sodium thiomethylate and stirred for 5 hours at 60° C. The mixture is stirred at room temperature for 18 hours, again treated with 1.0 g sodium thiomethylate and stirred for a further 6 hours at 60° C. After cooling, the mixture is poured into ice-water and extracted with ethyl acetate (3×). The combined organic phases are washed with water, dried (Na2SO4), filtered and concentrated. The residue obtained is chromatographically purified (hexane/ethyl acetate 2:1). 20.4 g (82 mmol, corresponding to 70% of theor.) of the product is obtained.

Workup

  1. stirringThe mixture is stirred at room temperature for 18 hours
  2. stirringstirred for a further 6 hours at 60° C
  3. temperatureAfter cooling
  4. extractionextracted with ethyl acetate (3×)
  5. washThe combined organic phases are washed with water
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue obtained
  10. customis chromatographically purified (hexane/ethyl acetate 2:1)
  11. custom20.4 g (82 mmol, corresponding to 70% of theor.) of the product is obtained

Sources & evidence

ORD record
ord-ba4198057e124a7d9fb4280a99667f3b
Source dataset
uspto-grants-2013_09
Patent number
US08524724B2

Linked notes

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