Urea → 2-Tert-butyl-5-nitrophenol

HRID 423794

反応式

HRID 423794 の反応式
[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]

参加物

7

反応物 4

HCID 1176UreaHCID 8261032-Tert-butyl-5-nitroanilineHCID 21910475Sulfuric acid hydrate (1:1)2 回HCID 23668193Sodium Nitrite2 回

生成物 1

HCID 219596172-Tert-butyl-5-nitrophenol収率 62%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 1118Sulfuric Acid溶媒

反応条件

温度
2.5 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-e05242a0ed654e2ca4698beb7fb63496
出典データセット
uspto-grants-2012_01
特許番号
US08101767B2

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