Potassium Carbonate → 4-[(Pyridin-2-yl)sulfanyl]aniline

HRID 2222308Notes

Reaction equation

HRID 2222308 reaction equation
FC(F)(F)[C:3]1[CH:4]=[C:5]([N+:16]([O-])=O)[CH:6]=[CH:7][C:8]=1[S:9][C:10]1[CH:15]=[CH:14]N=CC=1.SC1C=C[N:25]=[CH:24][CH:23]=1.FC1C=CC([N+]([O-])=O)=CC=1C(F)(F)F.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.CCOCC.O>[N:25]1[CH:24]=[CH:23][CH:14]=[CH:15][C:10]=1[S:9][C:8]1[CH:3]=[CH:4][C:5]([NH2:16])=[CH:6][CH:7]=1

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 949542-Fluoro-5-nitrobenzotrifluorideHCID 230230843-Trifluoromethyl-4-(4-pyridinylthio)nitrobenzeneHCID 178418431pyridine-4-thiol

Product 1

HCID 189716604-[(Pyridin-2-yl)sulfanyl]anilineYield 54%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

3-(Trifluoromethyl)-4-(4-pyridinylthio)nitrobenzene: A solution of 4-mercaptopyridine (2.8 g, 24 mmoles), 2-fluoro-5-nitrobenzotrifluoride (5 g, 23.5 mmoles), and potassium carbonate (6.1 g, 44.3 mmoles) in anhydrous DMF (80 mL) was stirred at room temperature and under argon overnight. TLC showed complete reaction. The mixture was diluted with Et2O (100 mL) and water (100 mL) and the aqueous layer was back-extracted with Et2O (2×100 mL). The organic layers were washed with a saturated NaCl solution (100 mL), dried (MgSO4), and concentrated under reduced pressure. The solid residue was triturated with Et2O to afford the desired product as a tan solid (3.8 g, 54%): TLC (30% EtOAc/70% hexane) Rf 0.06; 1H-NMR (DMSO-d6) δ 7.33 (dd, J=1.2, 4.2 Hz, 2H), 7.78 (d, J=8.7 Hz, 1H), 8.46 (dd, J=2.4, 8.7 Hz, 1H), 8.54-8.56 (m, 3H).

Workup

  1. customreaction
  2. extractionthe aqueous layer was back-extracted with Et2O (2×100 mL)
  3. washThe organic layers were washed with a saturated NaCl solution (100 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe solid residue was triturated with Et2O

Sources & evidence

ORD record
ord-9dacd276d3974ca79f026f796c28e7d9
Source dataset
uspto-grants-2008_05
Patent number
US07371763B2

Reaction notes

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