Allyl bromide → 3-(3,5-Dimethoxyphenyl)-1-propene

HRID 1750044

Reaktionsgleichung

Reaktionsgleichung von HRID 1750044
[Cu]C#N.[Cl-].[Li+].[CH3:6][O:7][C:8]1[CH:9]=[C:10]([Mg]Cl)[CH:11]=[C:12]([O:14][CH3:15])[CH:13]=1.[CH2:18](Br)[CH:19]=[CH2:20]>C1COCC1>[CH2:20]([C:10]1[CH:9]=[C:8]([O:7][CH3:6])[CH:13]=[C:12]([O:14][CH3:15])[CH:11]=1)[CH:19]=[CH2:18]

Komponenten

6

Edukt 4

HCID 7841Allyl bromideHCID 433294Lithium ChlorideHCID 178418546HCID 178418546, VerbindungHCID 178493478HCID 178493478, Verbindung

Produkt 1

HCID 5248743-(3,5-Dimethoxyphenyl)-1-propene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To a stirred solution of 1.49 g (16.5 mmol) of copper (I) cyanide and 1.39 g (33 mmol) of lithium chloride in 40 mL of THF was added dropwise 15 mL of a 1 M solution of 3,5-dimethoxyphenylmagnesium chloride in THF at −78° C. After stirring for 5 min, 2.5 mL (3.6 g, 30 mmol) of allyl bromide was added dropwise, and the resulting solution was stirred for 16 h while slowly warming to room temperature. The reaction mixture was quenched by slowly adding saturated NH4Cl(aq) and stirring for 5 min. The layers were separated and the aqueous phase was extracted three times with 50-mL portions ethyl acetate. The combined organic fractions were dried (Na2SO4), filtered through a pad of silica gel (eluted with ethyl acetate) and concentrated in vacuo. The residue was chromatographed over silica gel (eluted with 50:1 hexanes-ethyl acetate) to afford 2.59 g of a pale-yellow oil as a 6:1 mixture of 2:3. The mixture was suitable for further reactions without additional purification: 1H NMR (400 MHz, CDCl3) δ 6.36 (d, J=2.4 Hz, 2H), 6.32 (t, J=2.4 Hz, 1H), 6.81-5.87 (m, 1 H), 5.10 (dd, J=16.8, 1.6 Hz, 1 H), 5.07 (dd, J=9.6, 1.6 Hz, 1H), 3.78 (s, 6H), 3.33 (d, J=6.8 Hz, 2H).

Aufarbeitung

  1. stirringthe resulting solution was stirred for 16 h
  2. customThe reaction mixture was quenched by slowly adding saturated NH4Cl(aq)
  3. stirringstirring for 5 min
  4. customThe layers were separated
  5. extractionthe aqueous phase was extracted three times with 50-mL portions ethyl acetate
  6. dry with materialThe combined organic fractions were dried (Na2SO4)
  7. filtrationfiltered through a pad of silica gel (eluted with ethyl acetate)
  8. concentrationconcentrated in vacuo
  9. customThe residue was chromatographed over silica gel (eluted with 50:1 hexanes-ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-d0565107df2f4f13a500355fcf316e04
Quelldatensatz
uspto-grants-2015_10
Patentnummer
US09156836B2

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