5-Chloro-2-nitroaniline → 5-(Methylthio)-2-nitroaniline

HRID 1435122Notes

Reaction equation

HRID 1435122 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].[CH3:12][S-:13].[Na+]>CN(C=O)C.CCOC(C)=O>[CH3:12][S:13][C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7]

Participants

5

Reactant 2

HCID 742185-Chloro-2-nitroanilineHCID 4378561Sodium methanethiolate

Product 1

HCID 105354825-(Methylthio)-2-nitroanilineYield 81%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-Chloro-2-nitroaniline (15 g, 87.2 mmol) was dissolved in 250 mL of DMF with stirring. Sodium thiomethoxide (9.8 g, 140 mmol) was added and the reaction stirred at 65° C. for 20 h. The reaction was cooled to rt and diluted with EtOAc. then washed with water (5×), brine (1×), dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash chromatography to afford 12.9 g (81%) of 5-(methylthio)-2-nitroaniline as a red-orange solid. 1H NMR (400 MHz, DMSO-d6) δ 7.85 (d, J=8.97 Hz, 1H), 7.45 (br s, 2H), 6.78 (d, J=1.83 Hz, 1H), 6.47 (dd, J=1.83 and 9.16 Hz, 1H), 2.47 (s, 3H).

Workup

  1. stirringthe reaction stirred at 65° C. for 20 h
  2. washthen washed with water (5×), brine (1×)
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography

Sources & evidence

ORD record
ord-e5a5aa8c464741c5b3afc44cd048b4a8
Source dataset
uspto-grants-2009_11
Patent number
US07615643B2

Reaction notes

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