Triethylamine → trans-Ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3h-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate

HRID 1867263Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1867263
Cl/[C:2](=[N:8]/[NH:9][C:10]1[CH:15]=[C:14]([F:16])[CH:13]=[CH:12][C:11]=1[O:17][CH2:18]/[CH:19]=[CH:20]/[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)/[C:3]([O:5][CH2:6][CH3:7])=[O:4].C(N(CC)CC)C.CCOC(C)=O>C1(C)C=CC=CC=1>[F:16][C:14]1[CH:13]=[CH:12][C:11]2[O:17][CH2:18][C@@H:19]3[C@H:20]([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])=[N:8][N:9]3[C:10]=2[CH:15]=1

Komponenten

5

Edukt 3

HCID 8471TriethylamineHCID 8857Ethyl AcetateHCID 89029529ethyl (2E)-2-chloro-2-[[5-fluoro-2-[(E)-3-phenylprop-2-enoxy]phenyl]hydrazinylidene]acetate

Produkt 1

HCID 91552591trans-Ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3h-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Versuchsvorschrift

Ethyl (2E)-chloro[(5-fluoro-2-{[(2E)-3-phenylprop-2-enyl]oxy}phenyl)hydrazono]ethanoate (5-3, 3.1 g, 8.23 mmol) was dissolved in anhydrous toluene (20 mL) and treated with triethylamine (11.5 mL, 83 mmol). The reaction was heated at reflux for 24 h, and cooled. EtOAc (100 mL) was added and the organic layer was washed with 5% NaHCO3. The organic layer was dried (MgSO4), filtered and concentrated under reduced pressure. The crude was purified by flash column chromatography (120 g SiO2 Redisep, 0-30% EtOAc/hexanes gradient) to give pure trans-ethyl 8-fluoro-3-phenyl-3a,4-dihydro-3H-pyrazolo[5,1-c][1,4]benzoxazine-2-carboxylate (5-4). 1H NMR (300 MHz, CDCl3) δ 7.32 (m, 6H), 6.86 (dd, J=8.9, 5.0 Hz, 1H), 6.68 (app dt, J=7.9, 3.1 Hz, 1H), 4.34-4.12 (m, 5H), 3.62 (t, J=10.7 Hz, 1H), 1.23 (t, J=7.0 Hz, 2H); MS (M+H+, C19H17FN2O3) 340.1 found 340.4 required.

Aufarbeitung

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 24 h
  3. temperaturecooled
  4. washthe organic layer was washed with 5% NaHCO3
  5. dry with materialThe organic layer was dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe crude was purified by flash column chromatography (120 g SiO2 Redisep, 0-30% EtOAc/hexanes gradient)

Quellen und Nachweise

ORD-Eintrag
ord-3fe9cd8ca1bd42ff8980c56b7fe74c63
Quelldatensatz
uspto-grants-2009_12
Patentnummer
US07632833B2

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