Cesium carbonate → 1,2,4,5-Tetrahydro-benzo[d]azepine-3-carboxylic acid tert-butyl ester

HRID 472580Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 472580
ClC1N=C2C(C3C=CC=CC=3OC)=CC=CN2N=1.[C:19]([O:23][C:24]([N:26]1[CH2:32][CH2:31][C:30]2[CH:33]=[CH:34][C:35](N)=[CH:36][C:29]=2[CH2:28][CH2:27]1)=[O:25])([CH3:22])([CH3:21])[CH3:20].C1(P(C2CCCCC2)C2(P(C3CCCCC3)C3CCCCC3)CC=CC=C2C2C=CC=CC=2)CCCCC1.C(=O)([O-])[O-].[Cs+].[Cs+]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[C:19]([O:23][C:24]([N:26]1[CH2:32][CH2:31][C:30]2[CH:33]=[CH:34][CH:35]=[CH:36][C:29]=2[CH2:28][CH2:27]1)=[O:25])([CH3:22])([CH3:20])[CH3:21]

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 11402789Tert-butyl 7-amino-4,5-dihydro-1H-benzo[D]azepine-3(2H)-carboxylateHCID 674814532-Chloro-8-(2-methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridineHCID 866483582,2-Bis-dicyclohexylphosphanyl-biphenyl

Produkt 1

HCID 468356471,2,4,5-Tetrahydro-benzo[d]azepine-3-carboxylic acid tert-butyl esterAusbeute 141,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

To an oven-dried Schlenck flask under an atmosphere of argon was added 2-chloro-8-(2-methoxy-phenyl)-[1,2,4]triazolo[1,5-a]pyridine (0.460 g, 1.77 mmol), 7-amino-1,2,4,5-tetrahydro-3-benzazepine-3-carboxylic acid tert-butyl ester (0.558 g, 2.12 mmol), palladium acetate (0.0875 g, 0.390 mmol), 2,2-bis-dicyclohexylphosphanyl-biphenyl (0.242 g, 0.443 mmol), cesium carbonate (1.44 g, 4.43 mmol), followed by 1,4-dioxane (12.00 mL) and was degassed under an atmosphere of argon for 5 min and heated at 100° C. overnight, cooled at room temperature, diluted with dichloromethane, filtered through diatomaceous earth and concentrated. The reaction was purified via chromatography (silica gel 20%-30% ethyl acetate/hexanes) and concentrated to give 748-(2-methoxy-phenyl)[1,2,4]triazolo[1,5-a]pyridin-2-ylamino]-1,2,4,5-tetrahydro-3-benzazepine-3-carboxylic acid tert-butyl ester (0.744 g, 87%). 1H NMR (400 MHz, (D3C)2SO, δ, ppm): 9.54 (s, 1H), 8.78 (d, 1H), 7.55 (m, 2H), 7.45 (m, 2H), 7.35 (s, 1H) 7.15 (m, 1H), 7.05 (m, 3H), 3.74 (s, 3H), 3.48 (m, 4H), 2.78 (m, 4H), 1.41 (s, 9H): MS=486 (MH)+.

Aufarbeitung

  1. customwas degassed under an atmosphere of argon for 5 min
  2. temperaturecooled at room temperature
  3. additiondiluted with dichloromethane
  4. filtrationfiltered through diatomaceous earth
  5. concentrationconcentrated
  6. customThe reaction was purified via chromatography (silica gel 20%-30% ethyl acetate/hexanes)
  7. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-f836f29407764b8080ca65da2e58e9b6
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08633173B2

Notizen zur Reaktion

Wird geladen…