Tributylphosphine → Ethyl 5-fluoro-4-oxo-1,4-dihydrocinnoline-3-carboxylate

HRID 241983Notes

Reaction equation

HRID 241983 reaction equation
C(P(CCCC)CCCC)CCC.[N+:14](=[C:16]([C:22]([C:24]1[C:29](F)=[CH:28][CH:27]=[CH:26][C:25]=1[F:31])=[O:23])[C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N-:15]>O1CCCC1>[F:31][C:25]1[CH:26]=[CH:27][CH:28]=[C:29]2[C:24]=1[C:22](=[O:23])[C:16]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N:14][NH:15]2

Participants

4

Reactant 2

HCID 13831TributylphosphineHCID 86681842Ethyl 2-diazo-3-(2,6-difluorophenyl)-3-oxopropanoate

Product 1

HCID 68797377Ethyl 5-fluoro-4-oxo-1,4-dihydrocinnoline-3-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of tri-n-butylphosphine (8.6 g, 0.042 mol, 1.1 equiv) in anhydrous tetrahydrofuran (50 mL) was added to a tetrahydrofuran solution (150 mL) of ethyl 2-diazo-3-(2,6-difluorophenyl)-3-oxopropanoate (9.6 g, 0.038 mol). After stirring for 30 minutes at ambient temperature, the mixture was diluted with tetrahydrofuran (500 mL) and refluxed for 8 hours. The mixture was cooled to ambient temperature, concentrated in vacuo and purified by silica gel gradient chromatography (40:1; chloroform:methanol), providing the titled compound: 1H NMR (400 MHz, DMSO-d6) δ 13.85 (1H, br s), 7.78-7.75 (1H, m), 7.50-7.40 (1H, m), 7.27-7.14 (1H, m), 4.30 (2H, t, J=7.1 Hz), 1.30 (3H, t, J=7.1 Hz) ppm; low resolution mass spectrometry (APCI) m/z 237.0 [(M+H)+; calculated for C11H9FN2O3: 237.1].

Workup

  1. temperaturerefluxed for 8 hours
  2. temperatureThe mixture was cooled to ambient temperature
  3. concentrationconcentrated in vacuo
  4. custompurified by silica gel gradient chromatography (40:1; chloroform:methanol)

Sources & evidence

ORD record
ord-6e56afd2e2f84cb885b25bfbb7315241
Source dataset
uspto-grants-2014_02
Patent number
US08653079B2

Reaction notes

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