Acetic Acid → 4-[(Pyridin-2-yl)sulfanyl]aniline

HRID 2222309Notes

Reaction equation

HRID 2222309 reaction equation
FC(F)(F)[C:3]1[CH:4]=[C:5]([CH:7]=[CH:8][C:9]=1[S:10][C:11]1[CH:16]=[CH:15]N=CC=1)[NH2:6].FC(F)(F)C1C=C([N+]([O-])=O)C=CC=1SC1C=C[N:31]=[CH:30][CH:29]=1.C(O)(=O)C.[OH-].[Na+]>CCOCC.O.[Fe]>[N:31]1[CH:30]=[CH:29][CH:15]=[CH:16][C:11]=1[S:10][C:9]1[CH:3]=[CH:4][C:5]([NH2:6])=[CH:7][CH:8]=1

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 230230843-Trifluoromethyl-4-(4-pyridinylthio)nitrobenzeneHCID 23023094HCID 23023094, compound

Product 1

HCID 189716604-[(Pyridin-2-yl)sulfanyl]aniline

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

3-(Trifluoromethyl)-4-(4-pyridinylthio)aniline: A slurry of 3-trifluoromethyl-4-(4-pyridinylthio)nitrobenzene (3.8 g, 12.7 mmol), iron powder (4.0 g, 71.6 mmol), acetic acid (100 mL), and water (1 mL) were stirred at room temp. for 4 h. The mixture was diluted with Et2O (100 mL) and water (100 mL). The aqueous phase was adjusted to pH 4 with a 4 N NaOH solution. The combined organic layers were washed with a saturated NaCl solution (100 mL), dried (MgSO4), and concentrated under reduced pressure. The residue was filtered through a pad of silica (gradient from 50% EtOAc/50% hexane to 60% EtOAc/40% hexane) to afford the desired product (3.3 g): TLC (50% EtOAc/50% hexane) Rf 0.10; 1H-NMR (DMSO-d6) δ 6.21 (s, 2H), 6.84-6.87 (m, 3H), 7.10 (d, J=2.4 Hz, 1H), 7.39 (d, J=8.4 Hz, 1H), 8.29 (d, J=6.3 Hz, 2H). A3c. General Method for Substituted Aniline Formation Via Nitroarene Formation Through Nucleophilic Aromatic Substitution, Followed by Reduction

Workup

  1. washThe combined organic layers were washed with a saturated NaCl solution (100 mL)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated under reduced pressure
  4. filtrationThe residue was filtered through a pad of silica (gradient from 50% EtOAc/50% hexane to 60% EtOAc/40% hexane)

Sources & evidence

ORD record
ord-e8511032935a4546bfa5f75de0cfcabc
Source dataset
uspto-grants-2008_05
Patent number
US07371763B2

Reaction notes

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