2-Fluoroaniline → HCID 13922969, compound

HRID 1497333Notes

Reaction equation

HRID 1497333 reaction equation
[F:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].[C:9]([C:15]([O:17][CH3:18])=[O:16])#[C:10][C:11]([O:13][CH3:14])=[O:12]>CO>[F:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH:4]/[C:10](=[CH:9]/[C:15]([O:17][CH3:18])=[O:16])/[C:11]([O:13][CH3:14])=[O:12]

Participants

4

Reactant 2

HCID 95842-FluoroanilineHCID 12980Dimethyl acetylenedicarboxylate

Product 1

HCID 13922969HCID 13922969, compoundYield 83.4%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution 2-fluoroaniline (P1) (1.00 g, 9.00 mmol) in MeOH (11.1 mL) at 0° C. was added dimethyl acetylenedicarboxylate (P2) (DMAD, 1.34 mL, 10.8 mmol). The reaction was stirred at room temperature for 2 h. The mixture was concentrated and the residue was purified by silica gel flash chromatography (gradient 0-25% EtOAc in Hex) to give dimethyl (2E)-2-[(2-fluorophenyl)amino]but-2-enedioate (P3) (1.9 g, 83%). ES-MS [M+1]+=254.4. The above compound (1.90 g, 7.50 mmol) was dissolved in Eaton's reagent (8.00 mL, 50.4 mmol) and heated at 55° C. for 1 h. The LC-MS showed clean conversion. The reaction mixture was cooled to room temperature and slowly poured into a cold saturated solution of NaHCO3. The light-yellow precipitate formed was collected by filtration, washed with H2O and dried in vacuum to provide methyl 8-fluoro-4-hydroxyquinoline-2-carboxylate (P4) that gave a mass ion of 222.4 for M+H+.

Workup

  1. concentrationThe mixture was concentrated
  2. customthe residue was purified by silica gel flash chromatography (gradient 0-25% EtOAc in Hex)

Sources & evidence

ORD record
ord-4275b16e480d4af3a014ab00c5bd6d74
Source dataset
uspto-grants-2015_12
Patent number
US09199939B2

Reaction notes

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