Bromobenzene → 5-Cyclohex-1-enyl-3-phenylamino-thiophene-2-carboxylic acid methyl ester

HRID 1694463ノート

反応式

HRID 1694463 の反応式
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH2:16][CH2:15][CH2:14][CH2:13][CH:12]=2)=[CH:8][C:9]=1[NH2:10])=[O:4].Br[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.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>O1CCOCC1.C(Cl)Cl.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]>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:11]2[CH2:16][CH2:15][CH2:14][CH2:13][CH:12]=2)=[CH:8][C:9]=1[NH:10][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)=[O:4]

参加物

8

反応物 4

HCID 7961BromobenzeneHCID 10796Cesium carbonateHCID 634876Binap, (A+-)-HCID 577954015-Cyclohex-1-enyl-3-aminothiophene-2-carboxylic acid methyl ester

生成物 1

HCID 577953605-Cyclohex-1-enyl-3-phenylamino-thiophene-2-carboxylic acid methyl ester収率 76%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 6344Dichloromethane溶媒HCID 312751,4-Dioxane溶媒

実験手順

To a solution of 5-cyclohex-1-enyl-3-amino-thiophene-2-carboxylic acid methyl ester (111 mg, 0.47 mmol) and bromobenzene (54 μL, 0.51 mmol) in dry dioxane (3 mL) were added cesium carbonate (459 mg, 1.41 mmol) and Pd2 dba3 (43 mg, 0.047 mmol), and the mixture was deoxygenated by bubbling nitrogen through solution for 10 min. Then BINAP (47 mg, 0.075 mmol) was added to the mixture, and it was refluxed under nitrogen overnight. The mixture was diluted with CH2Cl2 and filtered through celite washing with CH2Cl2. Filtrate was concentrated under reduced pressure and purified by column chromatography on silica gel eluting with 2-30% EtOAc in hexanes to give 111 mg (76%) of 5-cyclohex-1-enyl-3-phenylamino-thiophene-2-carboxylic acid methyl ester.

後処理

  1. customthe mixture was deoxygenated
  2. customby bubbling nitrogen through solution for 10 min
  3. temperaturewas refluxed under nitrogen overnight
  4. filtrationfiltered
  5. washthrough celite washing with CH2Cl2
  6. concentrationFiltrate was concentrated under reduced pressure
  7. custompurified by column chromatography on silica gel eluting with 2-30% EtOAc in hexanes

出典と根拠

ORDレコード
ord-f80d7ba0be2c4cdabf5a81cdc401b9c6
出典データセット
uspto-grants-2012_04
特許番号
US08158675B2

反応ノート

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