Acetic Acid → (e)-11-(Bromomethylene)-3-fluoro-6,11-dihydrodibenzo[b,e]oxepine

HRID 244345Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 244345
C(OC(=O)[CH:5]=[C:6]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[CH2:10][O:9][C:8]2[CH:17]=[C:18]([F:21])[CH:19]=[CH:20][C:7]1=2)C.[OH-].[Li+].C(O)(=O)C.[Br:29]N1C(=O)CCC1=O>C(O)(C)C.O>[Br:29]/[CH:5]=[C:6]1/[C:7]2[CH:20]=[CH:19][C:18]([F:21])=[CH:17][C:8]=2[O:9][CH2:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]/1=2

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 3939Lithium HydroxideHCID 67184N-bromobutanimideHCID 67134827(3-fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester

Produkt 1

HCID 59468684(e)-11-(Bromomethylene)-3-fluoro-6,11-dihydrodibenzo[b,e]oxepineAusbeute 93,8 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 3776IsopropanolLösungsmittel

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

To a suspension of (3-fluoro-6H-dibenzo[b,e]oxepin-11-ylidene)-acetic acid ethyl ester (69.5 g, 0.23 mol) in isopropanol (725 mL) add a solution of lithium hydroxide (12.0 g, 0.53 mol) in water (125 mL) and warm to 70° C. for 4 h. Allow the mixture to cool to 40° C. and then treat with glacial acetic acid (0.44 mol, 25 mL). After stirring for 15 min, add N-bromosuccinimide (0.25 mol, 44 g). Bubbling ensues, the temperature rises to 45° C., and solids form after a few minutes. Stir the mixture at 40-45° C. for one hour and cool to room temperature. Add sodium bisulfite (4.5 g) in water (150 mL), saturated aqueous sodium bicarbonate (150 mL), and water (450 mL). Filter the resulting suspension and rinse with cold 1:1 isopropanol/water (300 mL). Dry the solid at 60° C./20 mm Hg overnight to obtain the title compound (65.8 g, 93%). 1H NMR (400 MHz, DMSO-d6) δ 4.9-5.4 (br d, 2H), 6.63 (dd, 1H), 6.77 (dt, 1H), 7.13 (s, 1H), 7.32-7.46 (m, 4H), 7.52 (dd, 1H).

Aufarbeitung

  1. temperatureAllow the mixture to cool to 40° C.
  2. customBubbling
  3. customrises to 45° C.
  4. waitsolids form after a few minutes
  5. stirringStir the mixture at 40-45° C. for one hour
  6. temperaturecool to room temperature
  7. filtrationFilter the resulting suspension
  8. washrinse with cold 1:1 isopropanol/water (300 mL)
  9. customDry the solid at 60° C./20 mm Hg overnight

Quellen und Nachweise

ORD-Eintrag
ord-ccc6ac4c04834afe901c4b20806f6d56
Quelldatensatz
uspto-grants-2014_02
Patentnummer
US08658638B2

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