Sodium Carbonate → HCID 57930979, Verbindung

HRID 1096919Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1096919
Br[C:2]1[CH:3]=[C:4]2[C:21](=[CH:22][CH:23]=1)[O:20][C:7]1([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:9][CH2:8]1)[CH2:6][C:5]2=[O:24].C(O[K])(C)=O.[C:30]([O:34][C:35](=[O:43])[C:36]1[CH:41]=[C:40](Br)[CH:39]=[N:38][CH:37]=1)([CH3:33])([CH3:32])[CH3:31].C([O-])([O-])=O.[Na+].[Na+]>O1CCOCC1.CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:30]([O:34][C:35](=[O:43])[C:36]1[CH:41]=[C:40]([C:2]2[CH:3]=[C:4]3[C:21](=[CH:22][CH:23]=2)[O:20][C:7]2([CH2:12][CH2:11][N:10]([C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH2:9][CH2:8]2)[CH2:6][C:5]3=[O:24])[CH:39]=[N:38][CH:37]=1)([CH3:33])([CH3:31])[CH3:32]

Komponenten

11

Edukt 4

HCID 10340Sodium CarbonateHCID 2794759tert-Butyl 6-bromo-4-oxospiro[chroman-2,4'-piperidine]-1'-carboxylateHCID 18422124tert-Butyl 5-bromonicotinateHCID 178476685HCID 178476685, Verbindung

Produkt 1

HCID 57930979HCID 57930979, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 167845palladium(II) acetateKatalysatorHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)KatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Tert-butyl 6-bromo-4-oxospiro[chroman-2,4′-piperidine]-1′-carboxylate (19.8 g, 50.0 mmol), bis(pinacolato)diboran (14.0 g, 55.0 mmol), Pd(OAc)2 (560 mg, 2.50 mmol), DPPF (2.77 g, 5.00 mmol), and AcOK (5.82 g, 60.0 mmol) were suspended in dioxane (250 mL) and heated at 100° C. for 10 hours. After cooling down to room temperature, 5-bromo-nicotinicacid tert-butyl ester (14.2 g, 55.0 mmol), Pd(PPh3)4 (5.78 g, 5.00 mmol) and 2M Na2CO3 aq. (125 mL, 250 mmol) were added to the reaction mixture; and then heated at 100° C. for 15 hours. The reaction mixture was diluted with EtOAc and H2O, organic layer was washed with brine and dried over MgSO4. After filtration, the solvents were removed in vacuo and the residue was purified by silica gel column chromatography (hexane/EtOAc=10/0 to 6/4) and the obtained brown solid was crystallized from EtOAc/hexane (1/1) to afford 5-{1′-tert-butoxycarbonyl-4-oxospiro[chroman-2,4′-piperidin]-6-yl}nicotinic acid tert-butyl ester as a pale yellow solid.

Aufarbeitung

  1. temperatureAfter cooling down to room temperature
  2. temperatureand then heated at 100° C. for 15 hours
  3. washwas washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationAfter filtration
  6. customthe solvents were removed in vacuo
  7. customthe residue was purified by silica gel column chromatography (hexane/EtOAc=10/0 to 6/4)
  8. customthe obtained brown solid was crystallized from EtOAc/hexane (1/1)

Quellen und Nachweise

ORD-Eintrag
ord-83d3ee3b363d43a79f701da9cc9dbc7f
Quelldatensatz
uspto-grants-2012_03
Patentnummer
US08138197B2

Notizen zur Reaktion

Wird geladen…