Ammonia → 2-(4-Ethoxy-2,3-difluorophenyl)-5-methylselenophene

HRID 1873395

Reaktionsgleichung

Reaktionsgleichung von HRID 1873395
[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[Se:11][CH:12]=[CH:13][CH:14]=2)=[C:6]([F:15])[C:5]=1[F:16])[CH3:2].[Li][CH2:18]CCC.CI.[Cl-].[NH4+].N>C(OCC)C>[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[Se:11][C:12]([CH3:18])=[CH:13][CH:14]=2)=[C:6]([F:15])[C:5]=1[F:16])[CH3:2]

Komponenten

7

Edukt 5

HCID 222AmmoniaHCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 594563012-(4-Ethoxy-2,3-difluorophenyl)selenopheneHCID 178418339Butyllithium

Produkt 1

HCID 594563262-(4-Ethoxy-2,3-difluorophenyl)-5-methylselenophene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 3283Diethyl EtherLösungsmittel

Reaktionsbedingungen

Temperatur
-70 °C

Versuchsvorschrift

6.25 g (20.7 mmol) of 2-(4-ethoxy-2,3-difluorophenyl)selenophene are initially introduced in 50 ml of diethyl ether, and 16.9 ml (26.9 mmol, 15% soln. in hexane) of n-BuLi are metered in rapidly. The mixture is heated under reflux for 25 min and subsequently cooled to −70° C. 7.0 ml (0.11 mol) of methyl iodide are added in one portion, and the mixture is warmed to RT and stirred for 22 h. Sat. ammonium chloride soln. and conc. ammonia soln. are added, and the batch is stirred vigorously for a few minutes. The organic phase is separated off, and the aqueous phase is extracted with MTBE. The combined organic phases are washed with 2 N hydrochloric acid and sat. sodium chloride soln. and dried using sodium sulfate. The solution is concentrated to dryness, and the residue is purified by column chromatography (SiO2, n-heptane:EtOAc=20:1→10:1→5:1). The further purification is carried out by recrystallisation from n-heptane; 2-(4-ethoxy-2,3-difluorophenyl)-5-methylselenophene is obtained as a colourless solid (m.p. 76° C.).

Aufarbeitung

  1. temperatureThe mixture is heated
  2. temperatureunder reflux for 25 min
  3. temperaturethe mixture is warmed to RT
  4. additionare added
  5. stirringthe batch is stirred vigorously for a few minutes
  6. customThe organic phase is separated off
  7. extractionthe aqueous phase is extracted with MTBE
  8. washThe combined organic phases are washed with 2 N hydrochloric acid and sat. sodium chloride soln
  9. customand dried
  10. concentrationThe solution is concentrated to dryness
  11. customthe residue is purified by column chromatography (SiO2, n-heptane:EtOAc=20:1→10:1→5:1)
  12. customThe further purification
  13. customis carried out by recrystallisation from n-heptane

Quellen und Nachweise

ORD-Eintrag
ord-1e9af0e9faf242e9be36623064f4ce62
Quelldatensatz
uspto-grants-2012_11
Patentnummer
US08304036B2

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