Water → Methyl 1H-pyrazolo[3,4-C]pyridine-5-carboxylate

HRID 2377069노트

반응식

HRID 2377069 반응식
[CH3:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[CH:3]=1.[NH2:15]C1C(C)=CC(C(OC)=O)=NC=1.N([O-])=O.[Na+].O>C1COCC1.[Pd].CC(O)=O>[NH:8]1[C:7]2=[CH:6][N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[CH:3]=[C:2]2[CH:1]=[N:15]1

참가 물질

8

반응물 4

HCID 962WaterHCID 20717632Methyl 4-methyl-5-nitropyridine-2-carboxylateHCID 23668193Sodium NitriteHCID 69199253Methyl 5-amino-4-methylpyridine-2-carboxylate

생성물 1

HCID 59855813Methyl 1H-pyrazolo[3,4-C]pyridine-5-carboxylate수율 80.5%

시약·촉매·용매 3

HCID 23938Palladium촉매HCID 176Acetic Acid용매HCID 8028Tetrahydrofuran용매

실험 절차

To a stirring solution of methyl 4-methyl-5-nitro-pyridine-2-carboxylate (3.00 g) in THF (40 mL) was added Pd/C catalyst (300 mg). The flask was evacuated and back-filled with hydrogen from a balloon three times and then stirred under hydrogen overnight. The mixture was filtered through Celite, and the filter cake was extracted several times with ethyl acetate. The combined organic extracts were concentrated and the resulting white powder (2.58 g, 100%) consisting of methyl 5-amino-4-methyl-pyridine-2-carboxylate was used in the next step without further purification and characterization. To a stirring solution of methyl 5-amino-4-methyl-pyridine-2-carboxylate (2.58 g, 15.53 mmol) in AcOH (60 mL), was added 2.0 M sodium nitrite in water (9.3 mL, 18.63 mmol) and the mixture was stirred for 4 h at room temperature. The acetic acid and other volatiles were removed at high vacuum, the resulting solid was suspended in water and filtered to give the title compound as a yellowish solid (2.18 g, 79% yield). 1HNMR (DMSO-d6): δ ppm 13.98 (bs, 1H), 9.10 (s, 1H), 8.57 (s, 1H), 8.39 (s, 1H), 3.88 (s, 3H). LCMS (API-ES M+Na+) 200.

후처리

  1. customThe flask was evacuated
  2. additionback-filled with hydrogen from a balloon three times
  3. filtrationThe mixture was filtered through Celite
  4. extractionthe filter cake was extracted several times with ethyl acetate
  5. concentrationThe combined organic extracts were concentrated
  6. customwas used in the next step without further purification and characterization
  7. stirringthe mixture was stirred for 4 h at room temperature
  8. customThe acetic acid and other volatiles were removed at high vacuum
  9. filtrationfiltered

출처 및 근거

ORD 기록
ord-0fad31592f39414885b0d0aa0f9b1861
출처 데이터셋
uspto-grants-2008_12
특허 번호
US07468375B2

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