Cesium carbonate → ethyl 1-phenyl-5-(phenylamino)-1H-pyrazole-3-carboxylate

HRID 2194706노트

반응식

HRID 2194706 반응식
[NH2:1][C:2]1[N:6]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)[N:5]=[C:4]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[CH:3]=1.I[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.O1CCCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.O>[C:7]1([N:6]2[C:2]([NH:1][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)=[CH:3][C:4]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=[N:5]2)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

참가 물질

10

반응물 4

HCID 10796Cesium carbonateHCID 11575IodobenzeneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 23630921Ethyl 5-amino-1-phenyl-1H-pyrazole-3-carboxylate

생성물 1

HCID 68410675ethyl 1-phenyl-5-(phenylamino)-1H-pyrazole-3-carboxylate수율 59%

시약·촉매·용매 5

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매HCID 8857Ethyl Acetate용매

반응 조건

온도
120 °C

실험 절차

Ethyl 5-amino-1-phenyl-1H-pyrazole-3-carboxylate (443 mg) synthesized according to the method described in WO2004/98589, iodobenzene (469 mg), cesium carbonate (1.2 g), tris(dibenzylideneacetone)dipalladium (0) (87 mg) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (111 mg) were suspended in toluene (10 mL) and tetrahydrofuran (2 mL), and the mixture was sufficiently deaerated, and stirred at 120° C. for 18 hr under an argon atmosphere. The reaction mixture was allowed to cool to room temperature, water and ethyl acetate were added, and the mixture was filtered through celite. The organic layer of the filtrate was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=7:1→3:1), and the obtained solid was washed with a mixed solvent of diisopropyl ether and ethyl acetate to give the title compound as a pale-red solid (yield 345 mg, yield 59%).

후처리

  1. temperatureto cool to room temperature
  2. filtrationthe mixture was filtered through celite
  3. washThe organic layer of the filtrate was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=7:1→3:1)
  7. washthe obtained solid was washed with a mixed solvent of diisopropyl ether and ethyl acetate

출처 및 근거

ORD 기록
ord-d7d949d52824457a8065cb5e86105f2a
출처 데이터셋
uspto-grants-2012_12
특허 번호
US08334301B2

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