Methyl quinoline-6-carboxylate → Methyl 2-tert-butylquinoline-6-carboxylate

HRID 1094649

Reaktionsgleichung

Reaktionsgleichung von HRID 1094649
[N:1]1[C:10]2[C:5](=[CH:6][C:7]([C:11]([O:13][CH3:14])=[O:12])=[CH:8][CH:9]=2)[CH:4]=[CH:3][CH:2]=1.[C:15]([Mg]Cl)([CH3:18])([CH3:17])[CH3:16]>C1COCC1.[O-2].[O-2].[Mn+4]>[C:15]([C:2]1[CH:3]=[CH:4][C:5]2[C:10](=[CH:9][CH:8]=[C:7]([C:11]([O:13][CH3:14])=[O:12])[CH:6]=2)[N:1]=1)([CH3:18])([CH3:17])[CH3:16]

Komponenten

5

Edukt 2

HCID 736812Methyl quinoline-6-carboxylateHCID 178418310HCID 178418310, Verbindung

Produkt 1

HCID 57458162Methyl 2-tert-butylquinoline-6-carboxylateAusbeute 27 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418406HCID 178418406, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel3×

Reaktionsbedingungen

Temperatur
-40 °C

Versuchsvorschrift

To a THF (20 ml) solution of methyl quinoline-6-carboxylate (984 mg, 5.26 mmol, J. O. C., 2002, 67, 7890) was added t-butylmagnesium chloride in THF (15.8 ml, 1M solution) dropwise at −78° C. over 30 min. The mixture was stirred at −78° C. for 30 minutes and at −40° C. for 30 minutes, then at room temperature for 1 hour. The reaction was quenched with saturated ammonium chloride aqueous solution (100 ml) and extracted with EtOAc (100 ml×2) which was dried over sodium sulfate. Then, filtration, evaporation gave yellow oil, which was solved in THF (50 ml) and manganese dioxide (1.83 g 15.8 mmol) was added there. After the mixture was stirred at room temperature for 2.5 hours, the precipitate was removed through a pad of Celite and washed with EtOAc. The filtrate was concentrated and purified through silica gel column chromatography eluting with Hexane/EtOAc (20:1) to furnish the title compound (348 mg, 27% yield) as a white solid. 1H NMR (300 MHz, CDCl3) δ ppm 1.48 (9H, s), 3.99 (3H, s), 7.59 (1H, d, J=8.8 Hz), 8.08 (1H, d, J=8.8 Hz), 8.17 (1H, d, J=8.8 Hz), 8.26 (1H, dd, J=2.2, 8.8 Hz), 8.55 (1H, d, J=2.2 Hz) MS (ESI): m/z 244 (M+H)+.

Aufarbeitung

  1. waitat room temperature for 1 hour
  2. customThe reaction was quenched with saturated ammonium chloride aqueous solution (100 ml)
  3. extractionextracted with EtOAc (100 ml×2) which
  4. dry with materialwas dried over sodium sulfate
  5. filtrationThen, filtration, evaporation
  6. customgave yellow oil, which
  7. stirringAfter the mixture was stirred at room temperature for 2.5 hours
  8. customthe precipitate was removed through a pad of Celite
  9. washwashed with EtOAc
  10. concentrationThe filtrate was concentrated
  11. custompurified through silica gel column chromatography
  12. washeluting with Hexane/EtOAc (20:1)

Quellen und Nachweise

ORD-Eintrag
ord-afbccdc6aeff4a95884c9b592d3be4ad
Quelldatensatz
uspto-grants-2012_03
Patentnummer
US08134004B2

Verknüpfte Notizen

Wird geladen…