Quinoline → 4-Cyano-3-nitrobenzoic acid

HRID 341890Notes

Reaction equation

HRID 341890 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].[N:14]1C2C(=CC=CC=2)C=C[CH:15]=1>Cl.O>[C:15]([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])#[N:14]

Participants

5

Reactant 2

HCID 7047QuinolineHCID 73204-Chloro-3-nitrobenzoic acid

Product 1

HCID 221685834-Cyano-3-nitrobenzoic acidYield 48%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

4-Chloro-3-nitrobenzoic acid (5.84 g, 29 mM), cuprous cyanide (5.2 g, 58 mM), cuprous chloride (0.96 g, 9.7 mM), and quinoline (6.9 ml, 58 mM) were heated under an argon atmosphere at 180° for 3.5 hours. After cooling, the mixture was dissolved in concentrated hydrochloric acid (60 ml), diluted with water (80 ml), and extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with aqueous NaH22PO4, brine, and dried over MgSO4. Crude product was purified by chromatography on silica, eluting with a mixture of dichloromethane/acetic acid (98:2), to give 4-cyano-3-nitrobenzoic acid (2.65 g, 48%). Nmr (DMSO-d6 : δ 8.31 (d, 1H); 8.41 (dd, 1H); 8.68 (d, 1H).

Workup

  1. temperatureAfter cooling
  2. extractionextracted with ethyl acetate (3×100 ml)
  3. washThe combined organic layers were washed with aqueous NaH22PO4, brine
  4. dry with materialdried over MgSO4
  5. customCrude product was purified by chromatography on silica
  6. washeluting with a mixture of dichloromethane/acetic acid (98:2)

Sources & evidence

ORD record
ord-875671bd7adb450db171eaf7926be111
Source dataset
uspto-grants-1999_01
Patent number
US05856321

Reaction notes

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