Urea → 2-Tert-butyl-5-nitrophenol

HRID 423794

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HRID 423794 반응식
[C:1]([C:5]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:6]=1N)([CH3:4])([CH3:3])[CH3:2].N([O-])=[O:16].[Na+].NC(N)=O.OS(O)(=O)=O.O>OS(O)(=O)=O.O>[C:1]([C:5]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:6]=1[OH:16])([CH3:4])([CH3:3])[CH3:2]

참가 물질

7

반응물 4

HCID 1176UreaHCID 8261032-Tert-butyl-5-nitroanilineHCID 21910475Sulfuric acid hydrate (1:1)2회HCID 23668193Sodium Nitrite2회

생성물 1

HCID 219596172-Tert-butyl-5-nitrophenol수율 62%

시약·촉매·용매 2

HCID 962Water용매HCID 1118Sulfuric Acid용매

반응 조건

온도
2.5 °C

실험 절차

To a mixture of 2-tert-butyl-5-nitroaniline (1.94 g, 10 mmol) in 40 mL of 15% H2SO4 was added dropwise a solution of NaNO2 (763 mg, 11.0 mmol) in water (3 mL) at 0° C. The resulting mixture was stirred at 0-5° C. for 5 min. Excess NaNO2 was neutralized with urea, then 5 mL of H2SO4—H2O (v/v 1:2) was added and the mixture was refluxed for 5 min. Three additional 5 mL aliquots of H2SO4—H2O (v/v 1:2) were added while heating at reflux. The reaction mixture was cooled to room temperature and extracted with EtOAc twice. The combined organic layers were washed with brine and dried over MgSO4. After removal of solvent, the residue was purified by column chromatography (0-10% EtOAc-Hexane) to give 2-tert-butyl-5-nitrophenol (C-1-a) (1.2 g, 62%). 1H NMR (400 MHz, CDCl3) δ 7.76 (dd,J=8.6, 2.2 Hz, 1H), 7.58 (d,J=2.1 Hz, 1H), 7.43 (d,J=8.6 Hz, 1H), 5.41 (s, 1H), 1.45 (s, 9H); HPLC ret. time 3.46 min, 10-99% CH3CN, 5 min run.

후처리

  1. temperaturethe mixture was refluxed for 5 min
  2. temperaturewhile heating
  3. temperatureat reflux
  4. temperatureThe reaction mixture was cooled to room temperature
  5. extractionextracted with EtOAc twice
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over MgSO4
  8. customAfter removal of solvent
  9. customthe residue was purified by column chromatography (0-10% EtOAc-Hexane)

출처 및 근거

ORD 기록
ord-e05242a0ed654e2ca4698beb7fb63496
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08101767B2

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