Toluene → HCID 66990508, Verbindung

HRID 454606

Reaktionsgleichung

Reaktionsgleichung von HRID 454606
[CH3:1][NH:2][CH2:3][CH2:4][N:5]1[CH2:9][CH2:8][CH2:7][CH2:6]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(C)C=CC=CC=1.[CH2:25]([O:32][C:33]1[CH:60]=[CH:59][C:58](Br)=[CH:57][C:34]=1[C:35]([NH:37][C:38]1[CH:50]=[C:49]([C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[CH:48]=[CH:47][C:39]=1[C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])=[O:36])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(Cl)(Cl)Cl.O>[CH2:25]([O:32][C:33]1[CH:60]=[CH:59][C:58]([N:2]([CH3:1])[CH2:3][CH2:4][N:5]2[CH2:9][CH2:8][CH2:7][CH2:6]2)=[CH:57][C:34]=1[C:35]([NH:37][C:38]1[CH:50]=[C:49]([C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[CH:48]=[CH:47][C:39]=1[C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])=[O:36])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Komponenten

10

Edukt 4

HCID 1140TolueneHCID 62657Potassium Phosphate, Tribasic3×HCID 295976Methyl(2-(pyrrolidin-1-yl)ethyl)amine3×HCID 66990333Tert-butyl 2-(2-(benzyloxy)-5-bromobenzamido)-4-phenylbenzoate

Produkt 1

HCID 66990508HCID 66990508, VerbindungAusbeute 59,6 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 167845palladium(II) acetateKatalysator3×HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator3×HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylKatalysator3×HCID 962WaterLösungsmittelHCID 6212ChloroformLösungsmittel

Versuchsvorschrift

N-Methyl-2-(pyrrolidin-1-yl)ethylamine (0.086 g), tripotassium phosphate (0.17 g), tris(dibenzylideneacetone)dipalladium(0) (2.5 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to a toluene (2.3 mL) solution of tert-butyl 2-(2-(benzyloxy)-5-bromobenzamido)-4-phenylbenzoate (0.15 g), followed by heating to reflux under a nitrogen atmosphere for 1 hour and 30 minutes. The reaction mixture was cooled to room temperature, and then N-methyl-2-(pyrrolidin-1-yl)ethylamine (0.017 g), tripotassium phosphate (0.029 g), tris(dibenzylideneacetone)dipalladium(0) (2.5 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to the reaction mixture, followed by heating to reflux under a nitrogen atmosphere for 7 hours and 30 minutes. The reaction mixture was cooled to room temperature, and then N-methyl-2-(pyrrolidin-1-yl)ethylamine (0.017 g), tripotassium phosphate (0.029 g), tris(dibenzylideneacetone)dipalladium(0) 2.5 mg, 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to the reaction mixture, followed by heating to reflux under a nitrogen atmosphere for 3 hours. The reaction mixture was cooled to room temperature, and water and chloroform were added thereto. The insoluble substance was removed by filtration. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [eluent: 100-90% chloroform/methanol] to obtain 0.097 g of tert-butyl 2-(2-(benzyloxy)-5-(methyl(2-(pyrrolidin-1-yl)ethyl)amino)benzamido)-4-phenylbenzoate.

Aufarbeitung

  1. temperatureby heating
  2. temperatureto reflux under a nitrogen atmosphere for 1 hour and 30 minutes
  3. temperatureby heating
  4. temperatureto reflux under a nitrogen atmosphere for 7 hours and 30 minutes
  5. temperatureThe reaction mixture was cooled to room temperature
  6. temperatureby heating
  7. temperatureto reflux under a nitrogen atmosphere for 3 hours
  8. temperatureThe reaction mixture was cooled to room temperature
  9. customThe insoluble substance was removed by filtration
  10. customThe organic layer was separated
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated under reduced pressure
  13. customThe obtained residue was purified by silica gel column chromatography [eluent: 100-90% chloroform/methanol]

Quellen und Nachweise

ORD-Eintrag
ord-2946131bcfc44099b0ec69157b34f300
Quelldatensatz
uspto-grants-2013_07
Patentnummer
US08492582B2

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