Diisopropylamine → HCID 57722998, Verbindung

HRID 1987034Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1987034
C([Li])CCC.C(NC(C)C)(C)C.[C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])[CH3:14].Br[CH2:22][C:23]1[C:24]([Cl:37])=[N:25][C:26]([Cl:36])=[CH:27][C:28]=1[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=1[Cl:35]>C1COCC1.[Cl-].[Na+].O.C(OCC)(=O)C.C(O)(=O)C>[Cl:37][C:24]1[C:23]([CH2:22][CH2:14][C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[C:28]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=2[Cl:35])[CH:27]=[C:26]([Cl:36])[N:25]=1

Komponenten

9

Edukt 4

HCID 7912DiisopropylamineHCID 10908tert-Butyl acetateHCID 57722989HCID 57722989, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 57722998HCID 57722998, VerbindungAusbeute 91 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 176Acetic AcidLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

n-Butyllithium in hexanes (1.6M, 18 ml, 28.8 mmol) was added to di-isopropylamine (4.1 ml, 29.25 mmol) in dry THF (200 ml) at −10° under nitrogen. After 5 min. the solution was cooled to −70° and tert-butyl acetate (3.9 ml, 28.93 mmol) added dropwise. After stirring at −70° for 15 min. under nitrogen, 3-(bromomethyl)-2,6-dichloro-4-(2-chlorophenyl)pyridine (2.44 g, 6.942 mmol) in dry THF (18 ml) was added dropwise over 10 min., and the mixture stirred at −70° for 1 h. Glacial acetic acid (2.3 ml) was added, the temperature allowed to rise to 22° and brine (200 ml) and ethyl acetate (100 ml) added. The phases were separated and the aqueous further extracted with ethyl acetate (150 ml). The extracts were dried (Na2SO4), evaporated in vacuo and the residue purified by flash chromatography over silica eluting with cyclohexane-ethyl acetate (100:0-50:50) to give the title compound as a viscous gum (2.44 g, 91%).

Aufarbeitung

  1. temperatureAfter 5 min. the solution was cooled to −70°
  2. stirringthe mixture stirred at −70° for 1 h
  3. customto rise to 22°
  4. customThe phases were separated
  5. extractionthe aqueous further extracted with ethyl acetate (150 ml)
  6. dry with materialThe extracts were dried (Na2SO4)
  7. customevaporated in vacuo
  8. customthe residue purified by flash chromatography over silica eluting with cyclohexane-ethyl acetate (100:0-50:50)

Quellen und Nachweise

ORD-Eintrag
ord-01837af03117470189c77db87251c528
Quelldatensatz
uspto-grants-2009_06
Patentnummer
US07550480B2

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