3-Nitroanisole → 6-Nitro-o-anisidine

HRID 983577

反応式

HRID 983577 の反応式
[N+:1]([C:4]1[CH:5]=[C:6]([O:10][CH3:11])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].Cl.CO[NH2:15].CC(C)([O-])C.[K+]>CN(C=O)C.[Cu]Cl>[NH2:15][C:5]1[C:6]([O:10][CH3:11])=[CH:7][CH:8]=[CH:9][C:4]=1[N+:1]([O-:3])=[O:2]

参加物

6

反応物 3

HCID 111403-NitroanisoleHCID 521874O-Methylhydroxylamine hydrochlorideHCID 23665647Potassium tert-butoxide

生成物 1

HCID 854916-Nitro-o-anisidine収率 50.5%

試薬・触媒・溶媒 2

HCID 62652Cuprous chloride触媒HCID 6228Dimethylformamide溶媒2 回

実験手順

A suspension of 3-nitroanisole (1.550 g, 10.12 mmol) and O-methylhydroxylamine hydrochloride (1.078 g, 12.91 mmol) in DMF (15 mL) was added to a cold (0° C.) solution of potassium tert-butoxide (5.870 g, 52.30 mmol) and copper(I) chloride (0.200 g, 2.02 mmol) in DMF (35 mL). The cooling bath was removed and the resultant slurry was stirred at room temperature for 6 hours. The reaction mixture was poured into saturated aqueous NH4Cl (50 mL) and the mixture was extracted with CH2Cl2 (4×50 mL). The combined organic extracts were dried (Na2SO4) and concentrated. Purification of the crude material by column chromatography on silica gel (5:1 hexanes-ethyl acetate) followed by radial chromatography on silica gel (2 mm plate, 5:1 hexanes-ethyl acetate) provided 0.860 g (50%) of 2-amino-3-methoxy-nitrobenzene as a red solid. 1H NMR (CDCl3) □ 3.92 (s, 3H), 6.44 (br s, 2H), 6.61 (dd, 1H, J=9.0, 9.0 Hz), 6.88 (d, 1H, J=9.0 Hz), 7.74 (d, 1H, J=9.0 Hz).

後処理

  1. customThe cooling bath was removed
  2. additionThe reaction mixture was poured into saturated aqueous NH4Cl (50 mL)
  3. extractionthe mixture was extracted with CH2Cl2 (4×50 mL)
  4. dry with materialThe combined organic extracts were dried (Na2SO4)
  5. concentrationconcentrated
  6. customPurification of the crude material by column chromatography on silica gel (5:1 hexanes-ethyl acetate)

出典と根拠

ORDレコード
ord-17bf48160a2c4b1b89c0ef358fe21e8d
出典データセット
uspto-grants-2005_03
特許番号
US06864265B2

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