Ethyl 3-bromo-4-chlorobenzoate → HCID 68507475, Verbindung

HRID 2410079

Reaktionsgleichung

Reaktionsgleichung von HRID 2410079
[CH3:1][C:2]([CH3:8])([CH3:7])[CH2:3][CH2:4][Mg]Cl.[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15](Br)[CH:14]=1)[CH3:10]>O1CCOCC1.C(OCC)C.[Cl-].[Cl-].[Zn+2].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:9]([O:11][C:12](=[O:21])[C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[C:15]([CH2:4][CH2:3][C:2]([CH3:8])([CH3:7])[CH3:1])[CH:14]=1)[CH3:10]

Komponenten

7

Edukt 2

HCID 12594300Ethyl 3-bromo-4-chlorobenzoateHCID 178444610HCID 178444610, Verbindung

Produkt 1

HCID 68507475HCID 68507475, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 3007855ZincchlorideKatalysatorHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 3283Diethyl EtherLösungsmittelHCID 312751,4-DioxaneLösungsmittel

Versuchsvorschrift

3,3-dimethyl-1-butylmagnesium chloride (8.00 mmol, 0.5 M THF, Platte Valley Scientific) was added dropwise to a solution of ZnCl2 (4.00 mmol, 1M diethyl ether, Aldrich) in 1,4-dioxane (15 mL) at ambient temperature. The mixture was stirred 30 minutes followed by addition of 3-bromo-4-chlorobenzoic acid ethyl ester (1.05 g, 3.99 mmol) and Pd(dppf)2Cl2 (131 mg, 0.160 mmol). The mixture was heated to reflux for 30 minutes, cooled to ambient temperature, diluted with diethyl ether and quenched with H2O. The mixture was filtered through celite and the filtrate was washed with brine, dried (Na2SO4), filtered and concentrated under reduced pressure. Flash chromatography eluting with 5% to 15% ethyl acetate/hexanes provided the title compound. 1H NMR (DMSO-d6) δ 7.89 (d, 1H), 7.78 (dd, 1H), 7.56 (d, 1H), 4.32 (q, 2H), 2.73 (m, 2H), 1.41 (m, 2H), 1.32 (t, 3H), 0.97 (s, 9H); MS (DCI+) m/z 286 (M+NH4)+, 269 (M+H)+.

Aufarbeitung

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 30 minutes
  3. customquenched with H2O
  4. filtrationThe mixture was filtered through celite
  5. washthe filtrate was washed with brine
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. washFlash chromatography eluting with 5% to 15% ethyl acetate/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-81b97b83705540a5a10363aab60a8aa5
Quelldatensatz
uspto-grants-2014_08
Patentnummer
US08815930B2

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