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

HRID 1513288ノート

反応式

HRID 1513288 の反応式
[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]

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 16212273Tetrabutylammonium chloride hydrate触媒HCID 6228Dimethylformamide溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-0f5f2d4831ea46ee91ff95671909be5e
出典データセット
uspto-grants-2012_07
特許番号
US08217065B2

反応ノート

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