Quinoline → 4-Cyano-3-nitrobenzoic acid

HRID 1392030Notes

Reaction equation

HRID 1392030 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 NaH2PO4, 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 (DNSO-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 NaH2PO4, 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-d5c8c7b5a5a041cc8159072fe5f76ccf
Source dataset
uspto-grants-2008_03
Patent number
US07342005B2

Reaction notes

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