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

HRID 1360792Notes

Reaction equation

HRID 1360792 reaction equation
[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]

Participants

7

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 16212273Tetrabutylammonium chloride hydrateCatalystHCID 6228DimethylformamideSolvent

Procedure

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 acetate/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) δ ppm 1.46 (s, 9H) 6.69 (d, J=16.04 Hz, 1H) 7.49 (d, J=16.04 Hz, 1H) 7.59 (t, J=1.89 Hz, 1H) 7.81 (d, J=1.77 Hz, 2H). 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) δ ppm 1.41 (s, 9H) 2.52 (s, 2H) 2.85 (s, 2H) 7.08 (s, 2H) 7.18 (s, 1H).

Workup

  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 acetate/n-heptanes

Sources & evidence

ORD record
ord-835bca6f2f2246a48d7e4748ea56c5ed
Source dataset
uspto-grants-2011_02
Patent number
US07879850B2

Reaction notes

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