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

HRID 2377058ノート

反応式

HRID 2377058 の反応式
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

参加物

6

反応物 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)

生成物 1

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

試薬・触媒・溶媒 1

HCID 5943Carbon Tetrachloride溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-f0c442728b194e8c934f3768192cb013
出典データセット
uspto-grants-2008_12
特許番号
US07468375B2

反応ノート

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