Acetonitrile → HCID 67818376, Verbindung

HRID 2284542Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2284542
[CH3:1][O:2][C:3]1[CH:44]=[C:43]([O:45][CH3:46])[CH:42]=[CH:41][C:4]=1[CH2:5][NH:6][C:7]1[C:8]2[CH:15]=[CH:14][N:13]([C@H:16]3[C@@H:20]4[O:21][C:22]([CH3:25])([CH3:24])[O:23][C@@H:19]4[C@@H:18]([CH2:26][N:27]([CH3:40])S(C4C=CC=CC=4[N+]([O-])=O)(=O)=O)[O:17]3)[C:9]=2[N:10]=[CH:11][N:12]=1.C(=O)([O-])[O-].[Cs+].[Cs+].C(#N)C.C1(S)C=CC=CC=1>>[CH3:1][O:2][C:3]1[CH:44]=[C:43]([O:45][CH3:46])[CH:42]=[CH:41][C:4]=1[CH2:5][NH:6][C:7]1[C:8]2[CH:15]=[CH:14][N:13]([C@H:16]3[C@H:20]4[C@H:19]([O:23][C:22]([CH3:25])([CH3:24])[O:21]4)[C@@H:18]([CH2:26][NH:27][CH3:40])[O:17]3)[C:9]=2[N:10]=[CH:11][N:12]=1

Komponenten

5

Edukt 4

HCID 6342AcetonitrileHCID 7969ThiophenolHCID 10796Cesium carbonateHCID 67814681HCID 67814681, Verbindung

Produkt 1

HCID 67818376HCID 67818376, VerbindungAusbeute 56,8 %

Versuchsvorschrift

A suspension of N-(((3aR,4R,6R,6aR)-6-(4-((2,4-dimethoxybenzyl)amino)-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxol-4-yl)methyl)-N-methyl-2-nitrobenzenesulfonamide (0.82 g, 1.2 mmol) and cesium carbonate (0.82 g, 2.5 mmol) in acetonitrile (23 mL, 440 mmol) was degassed by sparging with nitrogen gas for 10 minutes. The solution was treated dropwise with benzenethiol (0.26 mL, 2.5 mmol) and the mixture was allowed to stir at room temperature overnight. After 22 h, LCMS indicated the reaction was complete. The reaction mixture was partitioned between 60 mL 1N NaOH and 120 mL CH2Cl2, the layers separated and the aqueous phase was washed with three 25 mL portions of CH2Cl2. The combined organic phase was dried over MgSO4, filtered, and concentrated to an oil. The material was purified by flash chromatography (80 g silica gel, 0-5% 7N NH3 in CH3OH/CH2Cl2) to yield the title compound (320 mg, 54%) as a foam: MS (ESI+) for C24H31N5O6 m/z 470.1 (M+H)+; (ESI−) for C24H31N5O6 m/z 468.0 (M−H); HPLC purity 99% (ret. time, 2.67 min).

Aufarbeitung

  1. customwas degassed
  2. customby sparging with nitrogen gas for 10 minutes
  3. waitAfter 22 h
  4. customThe reaction mixture was partitioned between 60 mL 1N NaOH and 120 mL CH2Cl2
  5. customthe layers separated
  6. washthe aqueous phase was washed with three 25 mL portions of CH2Cl2
  7. dry with materialThe combined organic phase was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated to an oil
  10. customThe material was purified by flash chromatography (80 g silica gel, 0-5% 7N NH3 in CH3OH/CH2Cl2)

Quellen und Nachweise

ORD-Eintrag
ord-af41685274244fb580511d99550fcec4
Quelldatensatz
uspto-grants-2015_09
Patentnummer
US09145438B2

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