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

HRID 2377058노트

반응식

HRID 2377058 반응식
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

참가 물질

6

반응물 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)

생성물 1

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

시약·촉매·용매 1

HCID 5943Carbon Tetrachloride용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-f0c442728b194e8c934f3768192cb013
출처 데이터셋
uspto-grants-2008_12
특허 번호
US07468375B2

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