Diethyl Ether → HCID 46837781, Verbindung

HRID 1399532Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1399532
[CH3:1][C@H:2]1[C:7](=[O:8])[O:6][CH2:5][C:4]([CH3:10])([CH3:9])[NH:3]1.[C:11]1([CH3:19])[CH:16]=[CH:15][C:14]([Mg]Br)=[CH:13][CH:12]=1.[NH4+].[Cl-].CCOCC>C1COCC1>[CH3:1][C@H:2]1[C@@:7]([C:14]2[CH:15]=[CH:16][C:11]([CH3:19])=[CH:12][CH:13]=2)([OH:8])[O:6][CH2:5][C:4]([CH3:10])([CH3:9])[NH:3]1

Komponenten

6

Edukt 4

HCID 3283Diethyl EtherHCID 25517Ammonium ChlorideHCID 46837646HCID 46837646, VerbindungHCID 178418370HCID 178418370, Verbindung

Produkt 1

HCID 46837781HCID 46837781, VerbindungAusbeute 61,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A solution of morpholin-2-one 15 (270 mg, 1.88 mmol) in anhydrous THF (1.9 mL) was cooled to −78° C. and treated with p-tolylmagnesium bromide (1.2 equiv., 2.26 mmol, 2.26 mL, 1 M solution in THF) under an N2 atmosphere. After stirring the reaction mixture at −78° C. for 1.5 h, saturated aqueous solution of NH4Cl (30 mL) was added to the reaction vessel, and the mixture was allowed to warm to room temperature. Ether (30 mL) was added to the reaction flask, the organic layer was separated. The aqueous phase was extracted with ether (twice). The combined organic extracts were washed (water, brine), dried (Na2SO4) and concentrated. The residue was purified by column chromatography on silica gel using CH2Cl2 to CH2Cl2-MeOH (90:10) as the eluent to give 271 mg (41%) of 4j as a yellow foam: [α]22D +21.2° (c 0.9, CHCl3); 1H NMR (CDCl3) δ 7.47 (d, 2H, J=8.2 Hz), 7.16 (d, 2H, J=8.0 Hz), 3.85 (d, 1H, J=11.3 Hz), 3.40 (d, 1H, J=11.2 Hz), 3.20-3.07 (m, 1H), 2.35 (s, 3H), 1.39 (s, 3H), 1.08 (s, 3H), 0.81 (d, 3H, J=6.5 Hz); 13C NMR (CDCl3) δ 129.6, 128.60, 128.49, 125.9, 103.2, 96.2, 69.4, 53.9, 53.4, 49.6, 27.3, 22.8, 16.5; LCMS (ESI) m/z 236.3 [(M+H)+, M=C14H21NO2].

Aufarbeitung

  1. temperatureto warm to room temperature
  2. customthe organic layer was separated
  3. extractionThe aqueous phase was extracted with ether (twice)
  4. washThe combined organic extracts were washed (water, brine)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography on silica gel

Quellen und Nachweise

ORD-Eintrag
ord-d5def89b3b794c29a2e02608917b1c7a
Quelldatensatz
uspto-grants-2014_12
Patentnummer
US08906908B2

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