N-Boc-4-hydroxyaniline → tert-Butyl 4-(2-(methylamino)-3-nitropyridin-4-yl-oxy)phenylcarbamate

HRID 1864671노트

반응식

HRID 1864671 반응식
[C:1]([NH:8][C:9]1[CH:14]=[CH:13][C:12]([OH:15])=[CH:11][CH:10]=1)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].CC(C)([O-])C.[K+].Cl[C:23]1[CH:28]=[CH:27][N:26]=[C:25]([NH:29][CH3:30])[C:24]=1[N+:31]([O-:33])=[O:32]>CN(C=O)C>[CH3:30][NH:29][C:25]1[C:24]([N+:31]([O-:33])=[O:32])=[C:23]([O:15][C:12]2[CH:11]=[CH:10][C:9]([NH:8][C:1](=[O:2])[O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[CH:14][CH:13]=2)[CH:28]=[CH:27][N:26]=1

참가 물질

5

반응물 3

HCID 2756771N-Boc-4-hydroxyanilineHCID 23665647Potassium tert-butoxideHCID 249031234-Chloro-N-methyl-3-nitropyridin-2-amine

생성물 1

HCID 42625417tert-Butyl 4-(2-(methylamino)-3-nitropyridin-4-yl-oxy)phenylcarbamate수율 60%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

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온도
80 °C

실험 절차

N-Boc-4-hydroxyaniline (334 mg, 1.6 mmol) was dissolved in dry DMF (5 mL) and the solution was degassed by argon bubbling for 10 minutes. Potassium tert-butoxide (179 mg, 1.6 mmol) was added, and the stirring and argon bubbling continued for 50 minutes. 4-Chloro-N-methyl-3-nitropyridin-2-amine (260 mg, 1.4 mmol) was added to the reaction mixture. The reaction mixture was heated and stirred at 80° C. for 9 hours, under argon. The solvent was evaporated and the residue was extracted between DCM and aqueous NaOH 1M. The extraction was repeated twice, the organic layer was dried over MgSO4, and evaporated. The residue was purified by column chromatography (eluent gradient DCM to DCM:AcOEt 15:1) to afford the title compound (300 mg, 60%). 1H-NMR (δ, ppm, DMSO-d6): 1.48 (s, 9H, t-Bu), 2.91 (d, 3H, Me, J=4.60 Hz), 5.94 (d, 1H, HPy,5, J=5.70 Hz), 7.09 (d, 2H, Harom,Ph,3+5, J=9.00 Hz), 7.45 (m, 1H, NHPy), 7.53 (d, 2H, Harom,Ph,2+6), 8.07 (d, 1H, HPy,6), 9.46 (s, 1H, NH).

후처리

  1. customthe solution was degassed by argon bubbling for 10 minutes
  2. temperatureThe reaction mixture was heated
  3. customThe solvent was evaporated
  4. extractionthe residue was extracted between DCM and aqueous NaOH 1M
  5. extractionThe extraction
  6. dry with materialthe organic layer was dried over MgSO4
  7. customevaporated
  8. customThe residue was purified by column chromatography (eluent gradient DCM to DCM:AcOEt 15:1)

출처 및 근거

ORD 기록
ord-4e3e0c42a6fb4c2e8dc509ade7274c1c
출처 데이터셋
uspto-grants-2009_12
특허 번호
US07625922B2

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