Ethyl acetohydroximate → Ethyl-N-(4-benzyloxycarbonylphenoxy)acetimidate

HRID 971180Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 971180
[CH2:1]([O:3][C:4](=[N:6][OH:7])[CH3:5])[CH3:2].C(O[K])(C)(C)C.[CH2:14]([O:21][C:22](=[O:30])[C:23]1[CH:28]=[CH:27][C:26](F)=[CH:25][CH:24]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CN(C=O)C.O>[CH2:1]([O:3][C:4](=[N:6][O:7][C:26]1[CH:25]=[CH:24][C:23]([C:22]([O:21][CH2:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)=[O:30])=[CH:28][CH:27]=1)[CH3:5])[CH3:2]

Komponenten

6

Edukt 3

HCID 99894Ethyl acetohydroximateHCID 579322Benzyl 4-fluorobenzoateHCID 178418922HCID 178418922, Verbindung

Produkt 1

HCID 85420781Ethyl-N-(4-benzyloxycarbonylphenoxy)acetimidateAusbeute 107,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

To a stirring solution of ethyl-N-hydroxyacetimidate (3.79 g, 36.8 mmol) in anhydrous DMF (150 mL) under Ar was added tBuOK (4.09 g, 36.4 mmol) all at once. After 40 min benzyl-4-fluorobenzoate 17 (7.63 g, 17.9 mmol) was added and the reaction was stirred at room temperature. After 4 h the reaction was diluted with H2O (500 mL), extracted with EtOAc (4×100 mL), and the combined organics were washed with H2O (2×100 mL), dried over Na2SO4, filtered, and concentrated. Flash chromatographic purification over silica (5-10% gradient EtOAc in hexanes) afforded 19 as a clear syrup (6.02 g, 58%). 1H-NMR (500 MHz, CDCl3) δ 1.36 (t, J=7.0 Hz, 3H), 2.12 (s, 3H), 4.20 (q, J=7.0 Hz, 2H), 5.34 (s, 2H), 7.15-7.19 (m, 2H), 7.31-7.35 (m, 2H), 7.36-7.41 (m, 2H), 7.42-7.36 (m, 2H), 8.00-8.14 (m, 2H); 13C-NMR (125 MHz, CDCl3) δ 14.3, 14.4, 63.1, 66.4, 113.4, 122.9, 128.1, 128.1, 128.6, 131.5, 136.3, 163.5, 166.3, 166.4; GC-MS 228 m/z [M-85]+, benzyl-4-hydroxybenzoate C14H12O3 requires 228.

Aufarbeitung

  1. extractionextracted with EtOAc (4×100 mL)
  2. washthe combined organics were washed with H2O (2×100 mL)
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customFlash chromatographic purification over silica (5-10% gradient EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-1851956a35a548fab39d508984c27a31
Quelldatensatz
uspto-grants-2007_12
Patentnummer
US07312361B2

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