1,2-Dibromoethane → Ethyl 2-[5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphth-2-yl]benzoate

HRID 1376902

Reaktionsgleichung

Reaktionsgleichung von HRID 1376902
[Mg].Br[C:3]1[CH:12]=[CH:11][C:10]2[C:9]([CH3:14])([CH3:13])[CH2:8][CH2:7][C:6]([CH3:16])([CH3:15])[C:5]=2[CH:4]=1.BrCCBr.[CH2:21]([O:23][C:24](=[O:32])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1Br)[CH3:22]>C1COCC1.C(OCC)C.C(OC(=O)C)C.[Cl-].[Cl-].[Zn+2]>[CH3:13][C:9]1([CH3:14])[CH2:8][CH2:7][C:6]([CH3:16])([CH3:15])[C:5]2[CH:4]=[C:3]([C:30]3[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=3[C:24]([O:23][CH2:21][CH3:22])=[O:32])[CH:12]=[CH:11][C:10]1=2

Komponenten

8

Edukt 4

HCID 78391,2-DibromoethaneHCID 80186Ethyl 2-bromobenzoateHCID 2266856-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene2×HCID 5462224Magnesium

Produkt 1

HCID 18357939Ethyl 2-[5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphth-2-yl]benzoate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3007855ZincchlorideKatalysatorHCID 8028TetrahydrofuranLösungsmittel4×HCID 21584169Diethylether ethylacetateLösungsmittel

Versuchsvorschrift

To magnesium (180 mgs, 7.5 mmols) in THF (3 ml) was added a solution of 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (200 mgs) in THF (5 ml) followed by 1,2-dibromoethane (94 mgs, 0.5mmol). The mixture was stirred for 15 mins, then another portion of 2-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaph-thalene (1.14 g, 5 mmols) in THF (10 ml) was added. The mixture was stirred for 15 mins at room temperature, and refluxed for 1 h. ZnCl2 (680 mgs, 5 mmols) was added, stirred for 40 mins, and to the white precipitate. ethyl-2-bromobenzoate (1.09 g) in THF (5 ml) was added, immediately followed by addition of Ni(PPh2CH2CH2)Cl2 (26 mgs, 0.05 mmols). The mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with diethyl ether : ethylacetate (1:1, a total of 180 ml), the organic phase was washed with water (10 ml), brine (10 ml) NaHCO3 (10 ml) and brine (10 ml), dried (MgSO4) and the solvent was removed under reduced pressure. Silicagel chromatography (5% ethyl acetate in hexane) followed by HPLC purification of the crude material gave the title compound as a colorless oil.

Aufarbeitung

  1. stirringThe mixture was stirred for 15 mins at room temperature
  2. temperaturerefluxed for 1 h
  3. stirringstirred for 40 mins
  4. stirringThe mixture was stirred at room temperature for 16 h
  5. washa total of 180 ml), the organic phase was washed with water (10 ml), brine (10 ml) NaHCO3 (10 ml) and brine (10 ml)
  6. dry with materialdried (MgSO4)
  7. customthe solvent was removed under reduced pressure
  8. customSilicagel chromatography (5% ethyl acetate in hexane) followed by HPLC purification of the crude material

Quellen und Nachweise

ORD-Eintrag
ord-ca8b53d1bced447faefd559c9c29b891
Quelldatensatz
uspto-grants-1997_09
Patentnummer
US05663367

Verknüpfte Notizen

Wird geladen…