Potassium Carbonate → 4-(pyridin-4-ylsulfanyl)aniline

HRID 583818Notes

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([SH:8])=[CH:4][CH:3]=1.Cl.Cl[C:11]1[CH:16]=[CH:15][N:14]=[CH:13][CH:12]=1.C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.C(OCC)(=O)C.O>[N:14]1[CH:15]=[CH:16][C:11]([S:8][C:5]2[CH:6]=[CH:7][C:2]([NH2:1])=[CH:3][CH:4]=2)=[CH:12][CH:13]=1

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 4-aminothiophenol (20.2 g, 156.5 mmol) in anhydrous DMF (200 mL) was added 4-chloropyridine hydrochloride (24.4 g, 161.0 mmol) followed by potassium carbonate (44 g, 318.4 mmol). The reaction mixture was heated at 80° C. overnight, then diluted with ethyl acetate (400 mL) and water (400 mL). The aqueous layer was back-extracted with ethyl acetate (2×200 mL). The combined organic layers were washed with a saturated aqueous NaCl solution (200 mL), dried over anhy MgSO4, and concentrated under reduced pressure. The residue was filtered through a pad of silica with ethyl acetate and the resulting material was triturated with an ethyl ether/hexane solution to afford the desired product (24.7 g, 78%). TLC (50% ethyl acetate/50% hexane) Rf=0.25; 1H-NMR (DMSO-d6) δ 5.67 (bs, 2H), 6.65 (d, J=8.4 Hz, 2H), 6.88 (d, J=6.2 Hz, 2H), 7.19 (d, J=8.4 Hz, 2H), 8.27 (d, J=6.2 Hz, 2H), MS[M+H]+=203.

Workup

extractionThe aqueous layer was back-extracted with ethyl acetate (2×200 mL)
washThe combined organic layers were washed with a saturated aqueous NaCl solution (200 mL)
dry with materialdried over anhy MgSO4
concentrationconcentrated under reduced pressure
filtrationThe residue was filtered through a pad of silica with ethyl acetate
customthe resulting material was triturated with an ethyl ether/hexane solution

Sources & evidence

ORD record: ord-82fd50fb05e14ab599859b52e1d00d0b
Source dataset: uspto-grants-2005_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06924290B2

Reaction notes

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