Sodium hydride → 2-(4-Nitrophenyl)-4-tosylmorpholine

HRID 1473104Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1473104
[OH:1][CH:2]([C:15]1[CH:20]=[CH:19][C:18]([N+:21]([O-:23])=[O:22])=[CH:17][CH:16]=1)[CH2:3][NH:4][S:5]([C:8]1[CH:13]=[CH:12][C:11]([CH3:14])=[CH:10][CH:9]=1)(=[O:7])=[O:6].[H-].[Na+].FC(F)(F)S([O-])(=O)=O.Br[CH2:35][CH2:36][S+](C1C=CC=CC=1)C1C=CC=CC=1.[Cl-].[NH4+]>C(Cl)Cl.O.C(OCC)(=O)C>[N+:21]([C:18]1[CH:19]=[CH:20][C:15]([CH:2]2[O:1][CH2:36][CH2:35][N:4]([S:5]([C:8]3[CH:9]=[CH:10][C:11]([CH3:14])=[CH:12][CH:13]=3)(=[O:7])=[O:6])[CH2:3]2)=[CH:16][CH:17]=1)([O-:23])=[O:22]

Komponenten

8

Edukt 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 25193077(2-Bromoethyl)diphenylsulfonium TrifluoromethanesulfonateHCID 68282567N-(2-Hydroxy-2-(4-nitrophenyl)ethyl)-4-methylbenzenesulfonamide

Produkt 1

HCID 682828702-(4-Nitrophenyl)-4-tosylmorpholine

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

N-(2-Hydroxy-2-(4-nitrophenyl)ethyl)-4-methylbenzenesulfonamide (I84) (0.610 g, 1.34 mmol) was sonicated in DCM (20 mL) for five minutes and cooled to 0° C. under nitrogen. A 60% dispersion of NaH (0.220 g, 5.44 mmol) was added and the mixture stirred for five minutes before (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate (1.21 g, 2.72 mmol) was added. The mixture was stirred for 17 hours, allowing the cooling bath to come to room temperature over this time. Ethyl acetate (200 mL), saturated ammonium chloride (80 mL) and water (20 mL) were added and the layers separated. The aqueous phase was extracted with ethyl acetate (2×100 mL) and the combined ethyl acetate phases were washed with brine, dried (sodium sulfate) and evaporated. The residue was chromatographed (Isolera, 40 g silica cartridge, 0-40% ethyl acetate/petroleum benzine 40-60° C.) to give the title compound (I85) (433 mg, 88%) as a white solid; 1H NMR (400 MHz, CDCl3) δ 8.22-8.18 (m, 2H), 7.63-7.59 (m, 2H), 7.52-7.48 (m, 2H), 7.33 (dd, J=8.5, 0.6 Hz, 2H), 4.71 (dd, J=10.2, 2.6 Hz, 1H), 4.10 (ddd, J=11.6, 3.4, 1.4 Hz, 1H), 3.87 (td, J=11.6, 2.7 Hz, 1H), 3.82-3.77 (m, 1H), 3.65 (ddt, J=11.6, 2.8, 1.6 Hz, 1H), 2.51 (td, J=11.6, 3.4 Hz, 1H), 2.43 (s, 3H), 2.18 (dd, J=11.5, 10.3 Hz, 1H). LCMS

Aufarbeitung

  1. additionwas added
  2. customto come to room temperature over this time
  3. customthe layers separated
  4. extractionThe aqueous phase was extracted with ethyl acetate (2×100 mL)
  5. washthe combined ethyl acetate phases were washed with brine
  6. dry with materialdried (sodium sulfate)
  7. customevaporated
  8. customThe residue was chromatographed (Isolera, 40 g silica cartridge, 0-40% ethyl acetate/petroleum benzine 40-60° C.)

Quellen und Nachweise

ORD-Eintrag
ord-0b2bdb713b184aeaa6447b63c8d74e2a
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09012461B2

Notizen zur Reaktion

Wird geladen…