Methyl iodide → HCID 58929005, Verbindung

HRID 853648Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 853648
[CH:1]([O:14][C:15]1[C:16]2[C:35](=[O:36])[N:34]([CH2:37][C:38]3[CH:43]=[CH:42][C:41]([F:44])=[CH:40][CH:39]=3)[CH2:33][C:17]=2[C:18](OS(C(F)(F)F)(=O)=O)=[C:19]2[C:24]=1[N:23]=[CH:22][CH:21]=[CH:20]2)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:45]1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CI.[C:76]([O-:79])([O-])=[O:77].[Cs+].[Cs+]>CN(C=O)C.O.CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:45][O:79][C:76]([C:18]1[C:19]2[CH:20]=[CH:21][CH:22]=[N:23][C:24]=2[C:15]([O:14][CH:1]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[C:16]2[C:35](=[O:36])[N:34]([CH2:37][C:38]3[CH:39]=[CH:40][C:41]([F:44])=[CH:42][CH:43]=3)[CH2:33][C:17]=12)=[O:77]

Komponenten

9

Edukt 4

HCID 6328Methyl iodideHCID 10796Cesium carbonateHCID 812191,3-Bis(diphenylphosphino)propaneHCID 58928818HCID 58928818, Verbindung

Produkt 1

HCID 58929005HCID 58929005, VerbindungAusbeute 70 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 167845palladium(II) acetateKatalysatorHCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To trifluoro-methanesulfonic acid 9-benzhydryloxy-7-(4-fluoro-benzyl)-8-oxo-7,8-dihydro-6H-pyrrolo[3,4-g]quinolin-5-yl ester 46 (1.48 g, 2.39 mmol) and 1,3-bis(diphenylphosphino)propane (DPPP) (295 mg, 0.7 mmol) in DMF (20 mL) and water (1 mL) in a two-necked round bottom flask were added Pd(OAc)2 (107 mg, 0.48 mmol). The solution was degassed under high vacuum and flushed with carbon monoxide from a balloon. The flushing was repeated five times. TEA (0.733 mL, 3.26 mmol) was introduced. The mixture was heated under CO atmosphere for 2.5 hours and cooled down to the room temperature. MeI (0.74 mL, 12 mmol) and Cs2CO3 were added and stirring was continued under a nitrogen atmosphere for 45 minutes. The mixture was diluted with EtOAc (300 mL), washed with water, 1N aqueous HCl and brine, dried over MgSO4 and concentrated. The crude product was purified by chromatography on a silica gel column eluting with 15% to 35% of EtOAc in hexane to afford 9-benzhydryloxy-7-(4-fluoro-benzyl)-8-oxo-7,8-dihydro-6H-pyrrolo[3,4-g]quinoline-5-carboxylic acid methyl ester 212, (0.9 g, 1.69 mmol, 70%) as a yellow solid. 1H NMR (CDCl3): 89.25 (d, 1H), 9.05 (m, 1H), 7.80 (d, 4H), 7.56 (dd, 1H), 7.0-7.4 (m, 11H), 4.85 (s, 2H), 4.55 (s, 2H), 3.95 (s, 3H); MS: 555 (M+Na).

Aufarbeitung

  1. customThe solution was degassed under high vacuum
  2. customflushed with carbon monoxide from a balloon
  3. temperatureThe mixture was heated under CO atmosphere for 2.5 hours
  4. washwashed with water, 1N aqueous HCl and brine
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customThe crude product was purified by chromatography on a silica gel column
  8. washeluting with 15% to 35% of EtOAc in hexane

Quellen und Nachweise

ORD-Eintrag
ord-f46e6abdb0d44bfca51b69844906810f
Quelldatensatz
uspto-grants-2007_08
Patentnummer
US07253180B2

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