Cesium carbonate → HCID 67333799, Verbindung

HRID 2047589Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2047589
Br[C:2]1[C:3]([C:15]([O:17]CC)=[O:16])=[CH:4][C:5]([C:8]2[CH:9]=[N:10][CH:11]=[C:12]([CH3:14])[CH:13]=2)=[N:6][CH:7]=1.[NH:20]1[CH2:24][CH2:23][CH2:22][CH2:21]1.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.C(=O)([O-])[O-].[Cs+].[Cs+].[OH-].[Na+]>C1(C)C=CC=CC=1.CC([O-])=O.CC([O-])=O.[Pd+2].C1COCC1.CO>[CH3:14][C:12]1[CH:13]=[C:8]([C:5]2[CH:4]=[C:3]([C:15]([OH:17])=[O:16])[C:2]([N:20]3[CH2:24][CH2:23][CH2:22][CH2:21]3)=[CH:7][N:6]=2)[CH:9]=[N:10][CH:11]=1

Komponenten

9

Edukt 5

HCID 10796Cesium carbonateHCID 14798Sodium HydroxideHCID 31268PyrrolidineHCID 634876Binap, (A+-)-HCID 58394285Ethyl 5-bromo-5'-methyl-2,3'-bipyridine-4-carboxylate

Produkt 1

HCID 67333799HCID 67333799, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 1140TolueneLösungsmittelHCID 21899815MeOH tetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
135 °C

Versuchsvorschrift

To a solution of ethyl 5-bromo-5′-methyl-2,3′-bipyridine-4-carboxylate (2-1, 0.050 g, 0.156 mmol) in toluene (0.31 mL) at 25° C. was added pyrrolidine (0.026 mL, 0.311 mmol), BINAP (0.0096 g, 0.016 mmol) followed by Pd(OAc)2 (0.0035 g, 0.016 mmol) and cesium carbonate (0.076 g, 0.234 mmol) and the system was heated in the microwave reactor at 135° C. for 0.5 h. The system was partitioned between saturated aqueous sodium bicarbonate and EtOAc, washed with brine and dried over magnesium sulfate. Filtration and concentration followed by purification via normal phase chromatography (0→100% EtOAc in Hx) afforded a pale yellow oil. To this pale yellow oil (0.026 g, 0.083 mmol) in 1:1 THF/MeOH (0.40 mL) at 25° C. was added aqueous sodium hydroxide (0.0125 mL, 0.125 mmol, 10M) and the system was heated in the microwave reactor at 135° C. for 10 minutes. The solvents were removed in vacuo to afford the title compound (2-2) as a grey solid. ESI+MS C16H17N3O2: 284.2 found, 284.1 required.

Aufarbeitung

  1. customThe system was partitioned between saturated aqueous sodium bicarbonate and EtOAc
  2. washwashed with brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationFiltration and concentration
  5. customfollowed by purification via normal phase chromatography (0→100% EtOAc in Hx)
  6. customafforded a pale yellow oil
  7. temperaturethe system was heated in the microwave reactor at 135° C. for 10 minutes
  8. customThe solvents were removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-e9863e9e04614c1bb1760947f5ac6c82
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08592457B2

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