Ethyl Acetate → N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-N-(3-methoxypropyl)-2-nitrobenzenesulfonamide

HRID 85565Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 85565
[O:1]=[S:2]1(=[O:23])[CH2:7][CH2:6][N:5]([CH2:8][CH2:9][NH:10][S:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[N+:20]([O-:22])=[O:21])(=[O:13])=[O:12])[CH2:4][CH2:3]1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:31][CH2:32][CH2:33][O:34][CH3:35].C(OCC)(=O)C>CN(C=O)C.O>[O:23]=[S:2]1(=[O:1])[CH2:7][CH2:6][N:5]([CH2:8][CH2:9][N:10]([CH2:31][CH2:32][CH2:33][O:34][CH3:35])[S:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[N+:20]([O-:22])=[O:21])(=[O:12])=[O:13])[CH2:4][CH2:3]1

Komponenten

7

Edukt 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonate2×HCID 5245511-Bromo-3-methoxypropane2×HCID 68358008N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamide

Produkt 1

HCID 68358023N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-N-(3-methoxypropyl)-2-nitrobenzenesulfonamideAusbeute 109 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamide (0.400 g, 1.10 mmol) was combined with cesium carbonate (0.538 g, 1.65 mmol) in DMF (5 mL). The slurry was stirred at rt for 30 min, then to it was added 1-bromo-3-methoxypropane (0.337 g, 2.20 mmol). The resulting mixture was stirred at rt for 72 h. LCMS indicated incomplete conversion, so additional 1-bromo-3-methoxypropane (0.337 g, 2.20 mmol) and cesium carbonate (0.538 g, 1.65 mmol) were added and the mixture was heated to 70° C. for 1 hour. Dilution with ethyl acetate (60 mL) and water (40 mL) followed by shaking gave a separation of phases. The organic phase was isolated, washed with water (2×30 mL) and brine (25 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to a residue. Purification by silica gel chromatography (gradient 100% DCM to 60:1 DCM:MeOH) gave the title compound as a yellow oil (0.522 g, 109% yield). LCMS: m/z 436 (M+H+), retention time 1.50 min (method 11). 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 1.68-1.77 (m, 2H) 2.67 (t, J=6.26 Hz, 2H) 3.02 (br. s., 8H) 3.16 (s, 3H) 3.27 (t, J=5.80 Hz, 2H) 3.31-3.37 (m, 2H) 3.41 (t, J=6.26 Hz, 2H) 7.61-7.65 (m, 1H) 7.66-7.74 (m, 2H) 7.99-8.03 (m, 1H).

Aufarbeitung

  1. stirringThe resulting mixture was stirred at rt for 72 h
  2. additionwere added
  3. temperaturethe mixture was heated to 70° C. for 1 hour
  4. stirringby shaking
  5. customgave
  6. customa separation of phases
  7. customThe organic phase was isolated
  8. washwashed with water (2×30 mL) and brine (25 mL)
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo to a residue
  12. customPurification by silica gel chromatography (gradient 100% DCM to 60:1 DCM:MeOH)

Quellen und Nachweise

ORD-Eintrag
ord-580fcbe2d2e2403e97338c18cbf15d3e
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846647B2

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