Ethynylpyridine → 4-Nitro-2-(pyridin-2-ylethynyl)aniline

HRID 503372Notes

Reaction equation

I[C:2]1[CH:8]=[C:7]([N+:9]([O-:11])=[O:10])[CH:6]=[CH:5][C:3]=1[NH2:4].[C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1)#[CH:13]>CN(C=O)C.CCN(CC)CC.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[N+:9]([C:7]1[CH:6]=[CH:5][C:3]([NH2:4])=[C:2]([C:13]#[C:12][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)[CH:8]=1)([O-:11])=[O:10]

Participants

Conditions

Temperature: 60 °C

Procedure

To the solution of 2-iodo-4-nitroaniline (3.0 g, 11 mmol) in DMF (60 mL) and Et3N (60 mL) was added 2-ethynylpyridine (3.0 g, 45 mmol), Pd(PPh3)2Cl2 (600 mg) and CuI (200 mg) under N2. The reaction mixture was stirred at 60° C. for 12 h. The mixture was diluted with water and extracted with dichloromethane (3×100 mL). The combined organic layers were washed with brine, dried over anhydrous Na2SO4 and concentrated in vacuum. The residue was purified by chromatography on silica gel (5-10% ethyl acetate/petroleum ether) to afford 4-nitro-2-(pyridin-2-ylethynyl)aniline (1.5 g, 60%). 1H NMR (300 MHz, CDCl3) δ 8.60 (s, 1H), 8.13 (d, J=2.1 Hz, 1H), 7.98 (d, J=1.8, 6.9 Hz, 1H), 7.87-7.80 (m, 2H), 7.42-7.39 (m, 1H), 7.05 (brs, 2H), 6.80 (d, J=6.9 Hz, 1H).

Workup

extractionextracted with dichloromethane (3×100 mL)
washThe combined organic layers were washed with brine
dry with materialdried over anhydrous Na2SO4
concentrationconcentrated in vacuum
customThe residue was purified by chromatography on silica gel (5-10% ethyl acetate/petroleum ether)

Sources & evidence

ORD record: ord-17325209a9f74f01a8ffd46ac00df5bf
Source dataset: uspto-grants-2010_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07776905B2

Reaction notes

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