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

HRID 1190015Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1190015
[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]

Komponenten

8

Edukt 4

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

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysatorHCID 6344DichloromethaneLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

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.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-5ac8cb038f854bc383aa1ffc32dff29d
Quelldatensatz
uspto-grants-2014_03
Patentnummer
US08674118B2

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