Hydrochloric Acid → 4-Acetyl-2-fluorobenzonitrile

HRID 844019

Reaktionsgleichung

Reaktionsgleichung von HRID 844019
Br[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1.[CH:11]([O:13]CCCC)=[CH2:12].C(N(CC)CC)C.C([O-])(=O)C.[Tl+].Cl>CN(C)C=O.CC([O-])=O.CC([O-])=O.[Pd+2].C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:11]([C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[C:4]([F:10])[CH:3]=1)(=[O:13])[CH3:12]

Komponenten

10

Edukt 5

HCID 313Hydrochloric AcidHCID 8108Butyl vinyl etherHCID 8471TriethylamineHCID 11247thallium(I) acetateHCID 7360294-Bromo-2-fluorobenzonitrile

Produkt 1

HCID 224816534-Acetyl-2-fluorobenzonitrileAusbeute 76,6 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 812191,3-Bis(diphenylphosphino)propaneKatalysatorHCID 167845palladium(II) acetateKatalysator2×HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

A mixture of 4-Bromo-2-fluoro-benzonitrile (5.0 grams, 20.0 mmole), butyl vinyl ether (12.5 grams, 124.0 mmole), triethylamine (4.0 grams, 40.0 mmole), dppp (0.453 grams, 1.1 mmole), Thallium acetate (5.8 grams, 22.0 mmole) and Pd(OAc)2 (0.224 grams, 1.0 mmole) in dimethylformamide (50 ml) under N2 was heated to 90° C. for 3 hours. An additional 0.453 g dpp and 0.244 g Pd(OAc)2 was added and the mixture was heated to 90° C. for 4 hours. The mixture was cooled to room temperature, 25 ml 2 N hydrochloric acid was added and the mixture was stirred at room temperature for 30 hours. The mixture was poured into 300 ml water and extracted with diethyl ether. The combined extracts were washed with water and brine, dried over magnesium sulfate and concentrated to give an oil which was purified via flash chromatography on silica using 30% ethyl acetate/hexane as eluent to give an oil (2.5 g). 1H-NMR (CDCl3): δ2.63 (s, 3H), 7.73 (m, 2H), 7.81 (m, 1H).

Aufarbeitung

  1. temperaturethe mixture was heated to 90° C. for 4 hours
  2. temperatureThe mixture was cooled to room temperature
  3. extractionextracted with diethyl ether
  4. washThe combined extracts were washed with water and brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customto give an oil which
  8. customwas purified via flash chromatography on silica using 30% ethyl acetate/hexane as eluent

Quellen und Nachweise

ORD-Eintrag
ord-7471ca216a7e4abfbaca5ffb44d3da7c
Quelldatensatz
uspto-grants-2002_04
Patentnummer
US06380218B1

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