3-Nitroanisole → 6-Nitro-o-anisidine

HRID 747288

반응식

HRID 747288 반응식
[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]

참가 물질

6

반응물 3

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

생성물 1

HCID 854916-Nitro-o-anisidine수율 50.5%

시약·촉매·용매 2

HCID 62652Cuprous chloride촉매HCID 6228Dimethylformamide용매2회

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-912cbbbbe4694b538b8ba0bf555ba629
출처 데이터셋
uspto-grants-2008_07
특허 번호
US07396840B2

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