Hydrochloric Acid → 2-Fluoro-6-(1-methyleneethyl)anisole

HRID 1362464

Reaktionsgleichung

Reaktionsgleichung von HRID 1362464
Br[CH2:2]Br.[F:4][C:5]1[C:6]([O:14][CH3:15])=[C:7]([C:11](=O)[CH3:12])[CH:8]=[CH:9][CH:10]=1.Cl>C1COCC1.ClCCl.C(OCC)C.[Zn].[Ti](Cl)(Cl)(Cl)Cl.[Pb](Cl)Cl>[F:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:11](=[CH2:2])[CH3:12])[C:6]=1[O:14][CH3:15]

Komponenten

10

Edukt 3

HCID 313Hydrochloric AcidHCID 3024DibromomethaneHCID 112522251-(3-Fluoro-2-methoxyphenyl)ethanone

Produkt 1

HCID 669694642-Fluoro-6-(1-methyleneethyl)anisoleAusbeute 70,7 %

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 23994ZincKatalysatorHCID 24193Titanium TetrachlorideKatalysatorHCID 24459Lead chlorideKatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

41.8 g (639 mmol) of zinc dust and 874 mg (3.1 mmol) of lead(II) chloride are suspended in 557 ml of THF and at room temperature 39 ml (556 mmol) of dibromomethane are added. The mixture is stirred for a further 30 minutes and at 0° C. 68.8 ml (68.8 mmol) of a 1 M titanium(IV) chloride solution in dichloromethane are added dropwise. The cooling bath is removed and after 30 minutes at room temperature 13.6 g (80.8 mmol) of 1-(3-fluoro-2-methoxyphenyl)ethan-1-one (Chem. Commun. 2000, 14, 1323-4) in 139 ml of THF are added dropwise. The reaction mixture is stirred for a further 1.5 hours at room temperature. It is diluted with diethyl ether and cautiously poured onto a mixture of 4 M hydrochloric acid and ice. The phases are separated and subjected to extraction with diethyl ether, the extracts are washed with water and dried over sodium sulphate and the solvent is removed. The crude product is purified by column chromatography on silica gel (hexane/isopropyl ether 0-5%) to give 9.5 g of 2-fluoro-6-(1-methyleneethyl)anisole.

Aufarbeitung

  1. additionare added
  2. additionare added dropwise
  3. stirringThe reaction mixture is stirred for a further 1.5 hours at room temperature
  4. customThe phases are separated
  5. extractionsubjected to extraction with diethyl ether
  6. washthe extracts are washed with water
  7. dry with materialdried over sodium sulphate
  8. customthe solvent is removed
  9. customThe crude product is purified by column chromatography on silica gel (hexane/isopropyl ether 0-5%)

Quellen und Nachweise

ORD-Eintrag
ord-e239d1eb86ec481b83b76f703ea5ae4f
Quelldatensatz
uspto-grants-2011_02
Patentnummer
US07880042B2

Verknüpfte Notizen

Wird geladen…