Aniline → 4-Anilino-3-nitrobenzoic acid

HRID 1828167Notes

Reaction equation

HRID 1828167 reaction equation
Cl[C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=[O:7])=[CH:4][C:3]=1[N+:11]([O-:13])=[O:12].[NH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.CN1CCOCC1>[Cu].C(O)CC(C)C>[N+:11]([C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][C:2]=1[NH:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:6]([OH:8])=[O:7])([O-:13])=[O:12]

Participants

6

Reactant 3

HCID 6115AnilineHCID 73204-Chloro-3-nitrobenzoic acidHCID 79724-Methylmorpholine

Product 1

HCID 38243664-Anilino-3-nitrobenzoic acidYield 42.8%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 31260Isoamyl AlcoholSolvent

Procedure

A mixture of 4-chloro-3-nitrobenzoic acid (5.70 gm, 23 mmol), aniline (3.17 mL, 35 mmol), N-methylmorpholine (3.24 mL, 25 mmol), copper powder (0.1 gm, 1.57 mmol) and isoamyl alcohol (200 mL) was heated to reflux with stirring for 6 days. The mixture was then cooled to room temperature and filtered through a pad of celite. The filtrate was concentrated in vacuo and the residue taken up in ethyl acetate. The organic phase was washed with 3N HCl (2×1 L). The resulting organic phase was then extracted with saturated aqueous sodium carbonate solution. The aqueous phase was then washed with diethyl ether, followed by ethyl acetate. The aqueous phase was cautiously acidified to pH=1 with 6N HCl, and the resulting precipitate was filtered and dried to afford 2.54 gm of the title compound which was used without further purification.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. filtrationfiltered through a pad of celite
  4. concentrationThe filtrate was concentrated in vacuo
  5. washThe organic phase was washed with 3N HCl (2×1 L)
  6. extractionThe resulting organic phase was then extracted with saturated aqueous sodium carbonate solution
  7. washThe aqueous phase was then washed with diethyl ether
  8. filtrationthe resulting precipitate was filtered
  9. customdried

Sources & evidence

ORD record
ord-70b7a08323f14db3a00c03cbefa3def2
Source dataset
uspto-grants-2006_06
Patent number
US07056918B2

Reaction notes

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