Phenol → 4-Methoxy-1-nitro-2-phenoxybenzene

HRID 448383

反応式

HRID 448383 の反応式
[H-].[Na+].[C:3]1([OH:9])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.I[C:11]1[CH:12]=[C:13]([O:20][CH3:21])[CH:14]=[CH:15][C:16]=1[N+:17]([O-:19])=[O:18]>N1C=CC=CC=1.[Cu](Br)Br>[CH3:21][O:20][C:13]1[CH:14]=[CH:15][C:16]([N+:17]([O-:19])=[O:18])=[C:11]([O:9][C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=2)[CH:12]=1

参加物

6

反応物 3

HCID 996PhenolHCID 24758Sodium hydrideHCID 27334564-Nitro-3-iodoanisole

生成物 1

HCID 583072504-Methoxy-1-nitro-2-phenoxybenzene収率 64%

試薬・触媒・溶媒 2

HCID 24611Copper bromide (CuBr2)触媒HCID 1049Pyridine溶媒

実験手順

A 60% dispersion of sodium hydride (0.86 g, 22 mmol) was added to a mixture of copper bromide (2.6 g, 17.9 mmol) and phenol (1.7 g, 17.9 mmol) in pyridine (300 mL). After the effervescence subsided, the mixture was heated to reflux for 30 minutes. 3-Iodo-4-nitroanisole (5.0 g, 17.9 mmol) was added and stirring proceeded under nitrogen for 20 hours. The mixture was cooled and the reaction was quenched with saturated ammonium chloride (1 mL). The mixture was evaporated in vacuo. The residue was dissolved in ethyl acetate (250 mL) and washed with dilute aqueous HCl (2×200 mL), saturated sodium carbonate (2×200 mL) and water (200 mL), and was evaporated in vacuo. The residue was purified by ISCO silica gel flash chromatography in hexanes-ethyl acetate gradient, eluting 2.8 g of the product at 7:3 hexanes-ethyl acetate, in 64% yield; 1H NMR (CDCl3) δ 3.78 (s, 3H), 6.43 (d, J=2.3 Hz, 1H), 6.68 (dd, J=9.2, J=2.3 Hz, 1H), 7.03-7.07 (m, 2H), 7.19 (t, J=7.3 Hz, 1H), 7.37-7.41 (m, 2H), 8.07 (d, J=9.2 Hz, 1H).

後処理

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 30 minutes
  3. temperatureThe mixture was cooled
  4. customthe reaction was quenched with saturated ammonium chloride (1 mL)
  5. customThe mixture was evaporated in vacuo
  6. dissolutionThe residue was dissolved in ethyl acetate (250 mL)
  7. washwashed with dilute aqueous HCl (2×200 mL), saturated sodium carbonate (2×200 mL) and water (200 mL)
  8. customwas evaporated in vacuo
  9. customThe residue was purified by ISCO silica gel flash chromatography in hexanes-ethyl acetate gradient
  10. washeluting 2.8 g of the product at 7:3 hexanes-ethyl acetate

出典と根拠

ORDレコード
ord-5a118e78b6c842d58fa96ec98f1c6893
出典データセット
uspto-grants-2013_07
特許番号
US08481568B2

関連ノート

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