Cesium carbonate → 3-(3-Methoxy-phenylamino)-phthalic acid dimethyl ester

HRID 448409노트

반응식

HRID 448409 반응식
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10](I)[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7].C(=O)([O-])[O-].[Cs+].[Cs+].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.[CH3:68][O:69][C:70]1[CH:75]=[CH:74][CH:73]=[C:72]([NH2:76])[CH:71]=1>C1(C)C=CC=CC=1.C(Cl)Cl>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10]([NH:76][C:72]2[CH:73]=[CH:74][CH:75]=[C:70]([O:69][CH3:68])[CH:71]=2)[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7]

참가 물질

7

반응물 4

HCID 10796Cesium carbonateHCID 108243-MethoxyanilineHCID 634876Binap, (A+-)-HCID 2326127Dimethyl 3-iodophthalate

생성물 1

HCID 583072403-(3-Methoxy-phenylamino)-phthalic acid dimethyl ester수율 47%

시약·촉매·용매 2

HCID 1140Toluene용매HCID 6344Dichloromethane용매

실험 절차

A mixture of 3-iodo-phthalic acid dimethyl ester (1.0 g, 3.1 mmol), cesium carbonate (1.4 g, 4.3 mmol), Pd2(dba) (0.13 g, 0.14 mmol) and rac-BINAP (0.058 g, 0.093 mmol) in toluene (6 mL) was stirred at room temperature for 5 minutes. m-Anisidine (0.38 g, 3.1 mmol) was then added, and the reaction mixture was refluxed for 48 hours. The reaction mixture was diluted with methylene chloride (20 mL) and filtered through celite. The filter was washed with additional methylene chloride (25 mL). The combined filtrates were evaporated, and the residue was purified by ISCO silica gel flash chromatography using a hexanes-ethyl acetate gradient, eluting the product at 7:3 hexanes-ethyl acetate. It was then purified by preparative HPLC using an acetonitrile-water gradient, eluting the product at 6:4 acetonitrile:water to give the title product, 0.46 g in 47% yield; 1H NMR (CDCl3) δ 3.79 (s, 3H), 3.87 (s, 3H), 3.89 (s, 3H), 6.59-6.75 (m, 3H), 7.09-7.46 (m, 4H), 8.00 (s, 1H).

후처리

  1. temperaturethe reaction mixture was refluxed for 48 hours
  2. filtrationfiltered through celite
  3. washThe filter was washed with additional methylene chloride (25 mL)
  4. customThe combined filtrates were evaporated
  5. customthe residue was purified by ISCO silica gel flash chromatography
  6. washeluting the product at 7:3 hexanes-ethyl acetate
  7. customIt was then purified by preparative HPLC
  8. washeluting the product at 6:4 acetonitrile

출처 및 근거

ORD 기록
ord-ad2b172bc34b4986be1c2d375ad0537f
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08481568B2

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