tert-Butyl acrylate → 3-(3,5-Dichloro-phenyl)-acrylic acid tert butyl ester

HRID 1513288

Reaktionsgleichung

Reaktionsgleichung von HRID 1513288
[Cl:1][C:2]1[CH:3]=[C:4](I)[CH:5]=[C:6]([Cl:8])[CH:7]=1.[C:10]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])(=[O:13])[CH:11]=[CH2:12].C([O-])(=O)C.[K+]>CN(C=O)C.O.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:15]([O:14][C:10](=[O:13])[CH:11]=[CH:12][C:4]1[CH:3]=[C:2]([Cl:1])[CH:7]=[C:6]([Cl:8])[CH:5]=1)([CH3:18])([CH3:17])[CH3:16]

Komponenten

7

Edukt 3

HCID 15458tert-Butyl acrylateHCID 764241,3-Dichloro-5-iodobenzeneHCID 517044Potassium Acetate

Produkt 1

HCID 536582813-(3,5-Dichloro-phenyl)-acrylic acid tert butyl ester

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 16212273Tetrabutylammonium chloride hydrateKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

3,5-dichloro-iodo-benzene (5 g, 18 mmol) was stirred at room temperature as a solution in DMF (50 mL) containing tert butyl acrylate (6.5 mL, 2.5 eq), tetrabutyl ammonium chloride hydrate (5.1 g, 1 eq), potassium acetate (5.4 g, 3 eq) and palladium (II) acetate (-200 mg, 30 mol %) for 5 hours. Reaction mixture was reduced in vacuo, partitioned between water and ethyl acetate. Ethyl acetate fractions were dried over magnesium sulfate, filtered over a small plug of silica gel. Silica gel plug washed with 10% Ethyl aceated/n-heptanes to afford 3-(3,5-Dichloro-phenyl)-acrylic acid tert butyl ester after evaporation as a white solid. 1H NMR (400 MHz, DMSO-D6) ppm 1.46 (s, 9H) 6.69 (d, J=16.04 Hz, 1 H) 7.49 (d, J=16.04 Hz, 1 H) 7.59 (t, J=1.89 Hz, 1 H) 7.81 (d, J=1.77 Hz, 2 H). A solution of 3-(3,5-Dichloro-phenyl)-acrylic acid tert butyl ester (4 g, 14 mmol) in ethanol (100 mL) was charged with platinum oxide (800 mg), after purging reaction mixture with nitrogen. Attached balloon of hydrogen and stirred vigorously at room temperature over night. After removal of excess hydrogen, catalyst was removed by filtering mixture over a pad of celite and the resulting solution was evaporated to afford 3-(3,5-dichloro-phenyl)-propionic acid tert-butyl ester as an oil (3.8 g; 94% isolated yield). 1H NMR (400 MHz, CHLOROFORM-D) ppm 1.41 (s, 9H) 2.52 (s, 2 H) 2.85 (s, 2 H) 7.08 (s, 2 H) 7.18 (s, 1 H).

Aufarbeitung

  1. customReaction mixture
  2. custompartitioned between water and ethyl acetate
  3. dry with materialEthyl acetate fractions were dried over magnesium sulfate
  4. filtrationfiltered over a small plug of silica gel
  5. washSilica gel plug washed with 10% Ethyl

Quellen und Nachweise

ORD-Eintrag
ord-0f5f2d4831ea46ee91ff95671909be5e
Quelldatensatz
uspto-grants-2012_07
Patentnummer
US08217065B2

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