3-Methoxyaniline → 4-Hydroxy-7-methoxyquinoline-3-carbonitrile

HRID 396178Notes

Reaction equation

HRID 396178 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([NH2:9])[CH:6]=[CH:7][CH:8]=1.C([O:12][C:13](=O)[C:14]([C:19]#[N:20])=[CH:15]OCC)C>C(O)C>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6]([C:13](=[O:12])[C:14]([C:19]#[N:20])=[CH:15][NH:9]2)=[CH:7][CH:8]=1

Participants

4

Reactant 2

HCID 108243-MethoxyanilineHCID 789432-Propenoic acid, 2-cyano-3-ethoxy-, ethyl ester

Product 1

HCID 125594304-Hydroxy-7-methoxyquinoline-3-carbonitrileYield 63%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
256 °C

Procedure

An amount of 3-methoxy-phenylamine (45.3 g, 0.37 mol) and 2-cyano-3-ethoxy-acrylic acid ethyl ester (62.2 g, 0.37 mol), were heated at 120° C. for 0.5 hours, during which 14.4 mL of ethanol was collected by a Dean-Stark trap. To this was added a solution of biphenyl (333 mL) and phenyl ether (666 mL), and the mixture was heated at 256° C. for 6 hours, during which 22 mL of ethanol was collected by a Dean-Stark trap. The mixture was cooled to room temperature and filtered. The solid was washed with hexane and dried to give a brown solid (46.2 g, 63% yield), m.p 324-325° C.; 1H NMR (DMSO-d6) δ 12.63 (bs, 1H), 8.67 (s, 1H), 8.03 (d, J =9 Hz, 1H), 7.08 (dd, J=9 Hz, J=3 Hz, 1H), 7.01 (dd, J=3 Hz, 1H), 3.88 (s, 3H); HRMS (EI) m/z 223.04793 (M+Na); MS (ES) m/z 201.0 (M+1). Analysis for C11H8N2O2.0.1H2O: Found: C, 65.53; H, 4.09; N, 13.93. Calcd: C, 65.35; H, 4.06; N, 13.86.

Workup

  1. customwas collected by a Dean-Stark trap
  2. additionTo this was added a solution of biphenyl (333 mL) and phenyl ether (666 mL)
  3. customwas collected by a Dean-Stark trap
  4. temperatureThe mixture was cooled to room temperature
  5. filtrationfiltered
  6. washThe solid was washed with hexane
  7. customdried

Sources & evidence

ORD record
ord-90f3662dadec40debf97a12dd0cb7bde
Source dataset
uspto-grants-2003_08
Patent number
US06608048B2

Reaction notes

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