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

HRID 2110071Notes

Reaction equation

HRID 2110071 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-29f9c0902d4f4c4e87c161f34f83146b
Source dataset
uspto-grants-2009_04
Patent number
US07517880B2

Reaction notes

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