2-Bromopyridine → 4-cyano-2-nitro-N-(2-pyridyl)aniline

HRID 50921

Reaction equation

[C:1]([C:3]1[CH:9]=[CH:8][C:6]([NH2:7])=[C:5]([N+:10]([O-:12])=[O:11])[CH:4]=1)#[N:2].Br[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=1.C(=O)([O-])[O-].[K+].[K+]>[N+](C1C=CC=CC=1)([O-])=O>[C:1]([C:3]1[CH:9]=[CH:8][C:6]([NH:7][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][N:15]=2)=[C:5]([N+:10]([O-:12])=[O:11])[CH:4]=1)#[N:2]

Participants

Conditions

Temperature: 200 °C

Procedure

A mixture of 4-Cyano-2-nitroaniline (10.8 g, 66 mmol), 2-bromopyridine (12.6 g, 80 mmol), anhydrous potassium carbonate (9.12 g, 66 mmol) and copper-bronze (1.0 g, 15.7 mmol) in nitrobenzene (100 ml) was heated overnight at 200° C. The reaction mixture was cooled and filtered through a pad of celite. The filter cake was washed with dichloromethane (500 ml) and the filtrate was evaporated. The resultant residue was purified by column chromatography (silica gel, 500 g; n-hexane/ethyl acetate/dichloromethane (4/1/1)) to afford 7.28 g (46%) of 4-Cyano-2-nitro-N-(2-pyridyl)aniline as orange solids. 1H-NMR (CDCl3) δ: 10.53 (1H, br.s), 9.08 (1H, d, J=8.8 Hz), 8.58 (1H, d, J=8.8 Hz), 8.41 (1H, ddd, J=5.8, 1.8, 0.7 Hz), 7.78-7.69 (2H, m), 7.12-7.06 (1H, m), 7.02 (1H, d, J=8.8 Hz).

Workup

temperatureThe reaction mixture was cooled
filtrationfiltered through a pad of celite
washThe filter cake was washed with dichloromethane (500 ml)
customthe filtrate was evaporated
customThe resultant residue was purified by column chromatography (silica gel, 500 g; n-hexane/ethyl acetate/dichloromethane (4/1/1))

Sources & evidence

ORD record: ord-f75bca2fddeb400b818eb6ed12531c5e
Source dataset: uspto-grants-2004_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06713482B2

Linked notes

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