2-Chloro-1-fluoro-4-nitrobenzene → 2-Chloro-1-(methylsulfanyl)-4-nitrobenzene

HRID 1246618Notes

Reaction equation

HRID 1246618 reaction equation
F[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[Cl:11].[CH3:12][S-:13].[Na+]>CN(C=O)C.C(C1C(O)=CC(C)=C(SC2C=C(C(C)(C)C)C(O)=CC=2C)C=1)(C)(C)C>[Cl:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[S:13][CH3:12]

Participants

5

Reactant 2

HCID 676882-Chloro-1-fluoro-4-nitrobenzeneHCID 4378561Sodium methanethiolate

Product 1

HCID 105600942-Chloro-1-(methylsulfanyl)-4-nitrobenzeneYield 52.3%

Reagents, catalysts & solvents 2

HCID 7308SantonoxCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-fluoro-3-chloronitrobenzene (27 g, 156 mmol) in DMF (150 mL) at room temperature was added 5-tert-butyl-4-hydroxy-2-methylphenyl sulfide (100 mg) followed by sodium thiomethoxide (NaSMe) (10 g, 143 mmol) and the reaction was stirred for 6 h. The DMF was removed in vacuo and the residue was partitioned between ether (1 L) and water (1 L). The ether layer was washed with water (1 L) and brine (1 L), dried (MgSO4) and the solvent was removed under reduced pressure. The residue was purified by column chromatography (SiO2; DCM: pentane 1:5 increasing polarity to 3:7) to give the title compound (15.22 g, 49%) as a yellow solid; δH (400 MHz, CDCl3) 2.53 (3H, s), 7.20 (1H, d), 8.09 (1H, dd), 8.20 (1H, d).

Workup

  1. customThe DMF was removed in vacuo
  2. customthe residue was partitioned between ether (1 L) and water (1 L)
  3. washThe ether layer was washed with water (1 L) and brine (1 L)
  4. dry with materialdried (MgSO4)
  5. customthe solvent was removed under reduced pressure
  6. customThe residue was purified by column chromatography (SiO2; DCM: pentane 1:5 increasing polarity to 3:7)

Sources & evidence

ORD record
ord-a95ffb8ff0b54e9396eea89f92132f68
Source dataset
uspto-grants-2006_10
Patent number
US07129234B2

Reaction notes

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