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

HRID 1693068Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1693068
[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 ethyl acetate (100 ml×2) which was dried over sodium sulfate. Then, filtration and evaporation gave a yellow oil, which was dissolved in THF (50 ml) and manganese dioxide (1.83 g 15.8 mmol) was added. After the mixture was stirred at room temperature for 2.5 hours, the precipitate was removed through a pad of celite and washed with ethyl acetate. The filtrate was concentrated and purified through silica gel column chromatography, eluting with Hexane/Ethyl acetate (20:1), to furnish the title compound (348 mg, 27% yield) as a white solid. 1H NMR (300 MHz, CDCl3) δ 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 ethyl acetate (100 ml×2) which
  4. dry with materialwas dried over sodium sulfate
  5. filtrationThen, filtration and evaporation
  6. customgave a 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 ethyl acetate
  10. concentrationThe filtrate was concentrated
  11. custompurified through silica gel column chromatography
  12. washeluting with Hexane/Ethyl acetate (20:1)

Quellen und Nachweise

ORD-Eintrag
ord-ad3d2b778b184a95a1e83f324915f70e
Quelldatensatz
uspto-grants-2012_04
Patentnummer
US08158650B2

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