Hydrogen Peroxide → 1,3-Difluoro-2-methoxy-4-nitrobenzene

HRID 243236ノート

反応式

HRID 243236 の反応式
FC(F)(F)C(OC(=O)C(F)(F)F)=[O:4].OO.[F:16][C:17]1[C:22]([O:23][CH3:24])=[C:21]([F:25])[CH:20]=[CH:19][C:18]=1[NH2:26].[Cl-].[Na+].[OH2:29]>C(Cl)Cl>[F:25][C:21]1[CH:20]=[CH:19][C:18]([N+:26]([O-:4])=[O:29])=[C:17]([F:16])[C:22]=1[O:23][CH3:24]

参加物

6

反応物 4

HCID 784Hydrogen PeroxideHCID 9845Trifluoroacetic anhydrideHCID 38651622,4-Difluoro-3-methoxyanilineHCID 57417360Sodium chloride; water

生成物 1

HCID 681577701,3-Difluoro-2-methoxy-4-nitrobenzene収率 57%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

To a solution of trifluoroacetic anhydride (26.2 mL, 0.19 mol) in DCM (100 mL) at 0° C. was added, dropwise, hydrogen peroxide (50% in water, 12.9 mL, 0.17 mol) and the reaction mixture was stirred at 0° C. for 1.5 h. 2,4-Difluoro-3-methoxyphenylamine (3 g, 18.9 mmol) was added as a solution in DCM (20 mL) and the reaction mixture stirred at RT for 3 h. The reaction mixture was diluted with brine and extracted with DCM (3×30 mL). The combined organic fractions were washed with sat. aq. NaHCO3 solution, dried (MgSO4) and concentrated in vacuo. The resultant residue was subjected to flash chromatography (SiO2, eluting with 0-100% Et2O in cyclohexane) to give the title compound as a colourless solid (2.03 g, 57%). 1H NMR 400 MHz δ (CDCl3): 7.83-7.76 (1H, m), 7.03 (1H, td, J=9.4, 2.5 Hz), 4.08 (3H, t, J=1.1 Hz).

後処理

  1. extractionextracted with DCM (3×30 mL)
  2. washThe combined organic fractions were washed with sat. aq. NaHCO3 solution
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated in vacuo
  5. washThe resultant residue was subjected to flash chromatography (SiO2, eluting with 0-100% Et2O in cyclohexane)

出典と根拠

ORDレコード
ord-c99f3b63bec646a9971dad90cb26ee8c
出典データセット
uspto-grants-2014_02
特許番号
US08653089B2

反応ノート

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