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

HRID 2194706ノート

反応式

HRID 2194706 の反応式
[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

参加物

10

反応物 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

生成物 1

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

試薬・触媒・溶媒 5

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
120 °C

実験手順

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%).

後処理

  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

出典と根拠

ORDレコード
ord-d7d949d52824457a8065cb5e86105f2a
出典データセット
uspto-grants-2012_12
特許番号
US08334301B2

反応ノート

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