Diethyl Ether → Methyl 3H-imidazo[4,5-c]pyridine-6-carboxylate

HRID 2377058Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2377058
Cl.Cl.[N:3]1[C:11]2[CH2:10][C@@H:9]([C:12]([O:14][CH3:15])=[O:13])[NH:8][CH2:7][C:6]=2[NH:5][CH:4]=1.C(N(CC)CC)C.[Se](=O)=O.CCOCC>C(Cl)(Cl)(Cl)Cl>[N:3]1[C:11]2[CH:10]=[C:9]([C:12]([O:14][CH3:15])=[O:13])[N:8]=[CH:7][C:6]=2[NH:5][CH:4]=1

Komponenten

6

Edukt 4

HCID 3283Diethyl EtherHCID 8471TriethylamineHCID 24007Selenium DioxideHCID 14403671Methyl (6S)-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylate--hydrogen chloride (1/2)

Produkt 1

HCID 21892231Methyl 3H-imidazo[4,5-c]pyridine-6-carboxylateAusbeute 47 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 5943Carbon TetrachlorideLösungsmittel

Versuchsvorschrift

Methyl (6S)-4,5,6,7-tetrahydro-3H-imidazo[4,5-c]pyridine-6-carboxylate dihydrochloride (156.5 g, 0.62 mol), triethylamine (445.0 g, 4.4 mol, 7.0 mol eqv.), selenium dioxide (158.2 g, 1.43 mol, 2.3 mol eqv.), and polyphosphatesilyl ether (PPSE) (15.0 g) were added to CCl4 (1.5 L). The mixture was refluxed for 6 h. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was suspended in methanol (1.5 L), and triethylamine was added to adjust to pH 8. The brown solid was filtered and washed well with methanol. This brown solid (117.0 g) was recrystallized from hot DMF (2 L, 140° C.). The solution was filtered hot to remove black side products. Upon cooling to room temperature, the desired product crystallized out as a yellow solid (51.3 g, 47% yield, 95% pure). 1H NMR (DMSO-d6): δ 13.20 (br s, 1H), 9.02 (s, 1H), 8.58 (s, 1H), 8.31 (s, 1H), 3.89 (s, 3H); LCMS: Rt=1.33 min, and M+1=178.1 u/e.

Aufarbeitung

  1. temperatureThe mixture was refluxed for 6 h
  2. customthe solvent was removed under reduced pressure
  3. additiontriethylamine was added
  4. filtrationThe brown solid was filtered
  5. washwashed well with methanol
  6. customThis brown solid (117.0 g) was recrystallized from hot DMF (2 L, 140° C.)
  7. filtrationThe solution was filtered hot
  8. customto remove black side products
  9. temperatureUpon cooling to room temperature
  10. customthe desired product crystallized out as a yellow solid (51.3 g, 47% yield, 95% pure)

Quellen und Nachweise

ORD-Eintrag
ord-f0c442728b194e8c934f3768192cb013
Quelldatensatz
uspto-grants-2008_12
Patentnummer
US07468375B2

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