Acetic Acid → (2-Amino-5-bromophenyl)(4-fluorophenyl)methanone

HRID 1272778Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1272778
[F:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](Cl)=[O:7])=[CH:4][CH:3]=1.[Br:11][C:12]1[CH:18]=[CH:17][C:15]([NH2:16])=[CH:14][CH:13]=1.S(=O)(=O)(O)O.C(O)(=O)C>[Cl-].[Zn+2].[Cl-].O>[NH2:16][C:15]1[CH:17]=[CH:18][C:12]([Br:11])=[CH:13][C:14]=1[C:6]([C:5]1[CH:9]=[CH:10][C:2]([F:1])=[CH:3][CH:4]=1)=[O:7]

Komponenten

7

Edukt 4

HCID 176Acetic AcidHCID 1118Sulfuric Acid2×HCID 78074-BromoanilineHCID 678794-Fluorobenzoyl chloride

Produkt 1

HCID 1359860(2-Amino-5-bromophenyl)(4-fluorophenyl)methanoneAusbeute 46,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3007855ZincchlorideKatalysatorHCID 962WaterLösungsmittel2×

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

To neat 4-fluorobenzoyl chloride (50.00 g, 315 mmol) in a flask at 130° C. was added 4-bromoaniline (17.00 g, 100 mmol) in several portions. After it was stirred at 130° C. for 1 hour and the temperature was raised to 190° C., to the reaction mixture was added zinc chloride (11.00 g, 80.7 mmol) in several portions, then it was heated at 220° C. for 22 hours. Once cooled to 180° C., to the mixture was carefully added concentrated sulfuric acid (50 mL), acetic acid (70 mL), water (70 mL), and another portion of sulfuric acid (50 mL). The mixture was heated at 120° C. overnight. It was poured into water (500 mL) and a white solid was precipitated. It was collected by filtration and was dissolved in ethyl acetate and washed with 5% sodium carbonate until pH of the aqueous phase reached 8. The filtrate was basified with sodium carbonate and extracted with ethyl acetate. The combined ethyl acetate layers were dried over magnesium sulfate, filtered, and concentrated. The residue was then purified by chromatography (SiO2, 15–20% ethyl acetate/hexane) to provide the title compound (13.64 g, 46% yield). 1H NMR (CDCI3) δ 7.67 (m, 2H), 7.51 (d, 1H), 7.37 (dd, 1H), 7.14–7.20 (m, 2H), 6.65 (d, 1H), 6.02 (br s, 2H); ES-MS (m/z) 296 [M+3]+, 294 [M+1]+.

Aufarbeitung

  1. temperaturethe temperature was raised to 190° C., to the reaction mixture
  2. temperatureit was heated at 220° C. for 22 hours
  3. temperatureOnce cooled to 180° C., to the mixture
  4. temperatureThe mixture was heated at 120° C. overnight
  5. customa white solid was precipitated
  6. filtrationIt was collected by filtration
  7. dissolutionwas dissolved in ethyl acetate
  8. washwashed with 5% sodium carbonate until pH of the aqueous phase
  9. extractionextracted with ethyl acetate
  10. dry with materialThe combined ethyl acetate layers were dried over magnesium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated
  13. customThe residue was then purified by chromatography (SiO2, 15–20% ethyl acetate/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-0a091f5589064e33a10cd7020954a643
Quelldatensatz
uspto-grants-2007_04
Patentnummer
US07208513B2

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