4-Bromoanisole → 2-Methoxy-6-(4-methoxyphenyl)-8-methylquinoline

HRID 568351Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 568351
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=1.Br[C:16]1[CH:17]=[C:18]2[C:23](=[C:24]([CH3:26])[CH:25]=1)[N:22]=[C:21]([O:27][CH3:28])[CH:20]=[CH:19]2>CCCCCC.C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:28][O:27][C:21]1[CH:20]=[CH:19][C:18]2[C:23](=[C:24]([CH3:26])[CH:25]=[C:16]([C:7]3[CH:12]=[CH:11][C:10]([O:13][CH3:14])=[CH:9][CH:8]=3)[CH:17]=2)[N:22]=1

Komponenten

8

Edukt 3

HCID 77304-BromoanisoleHCID 14220967HCID 14220967, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 201504532-Methoxy-6-(4-methoxyphenyl)-8-methylquinoline

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 3007855ZincchlorideKatalysatorHCID 178418397HCID 178418397, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Versuchsvorschrift

n-Butyllithium (33.3 cm3 of a 1.5M solution in n-hexane) was added dropwise at -70° to a stirred solution of 4-bromoanisole (6.26 cm3) in THF (70 cm3) under nitrogen. After ten minutes, a solution of anhydrous zinc chloride (6.814 g) in THF (50 cm3) was added and the mixture was allowed to warm to room temperature over 0.5 hour. A mixture of 6-bromo-2-methoxy-8-methylquinoline (12.8 g) and tetrakis(triphenylphosphine)palladium (0) (0.5 g) was added and the mixture heated under reflux for 2 hours. Volatile material was removed in vacuo and the residue was partitioned between chloroform (150 cm3) and a solution of ethylenediaminetetraacetic acid (40 g) in water (250 cm3). The organic layer was dried (MgSO4) and evaporated to afford an oil which was chromatographed on silica (Merck "MK 60.9385" [Trade Mark]) eluting with hexane:ethyl acetate, 19:1. Combination and evaporation of the appropriate fractions afforded the title compound (5.49 g). A small portion of this was recrystallised from methanol and had m.p. of 104°-106° and the following analysis:

Aufarbeitung

  1. waitAfter ten minutes
  2. additionwas added
  3. temperaturethe mixture heated
  4. temperatureunder reflux for 2 hours
  5. customVolatile material was removed in vacuo
  6. customthe residue was partitioned between chloroform (150 cm3)
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customevaporated
  9. customto afford an oil which
  10. customwas chromatographed on silica (Merck "MK 60.9385" [Trade Mark])
  11. washeluting with hexane
  12. customCombination and evaporation of the appropriate fractions

Quellen und Nachweise

ORD-Eintrag
ord-32b1d0fb7a894ede8724d19645242259
Quelldatensatz
uspto-grants-1988_03
Patentnummer
US04728654

Notizen zur Reaktion

Wird geladen…