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

HRID 1513288

반응식

HRID 1513288 반응식
[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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 16212273Tetrabutylammonium chloride hydrate촉매HCID 6228Dimethylformamide용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-0f5f2d4831ea46ee91ff95671909be5e
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08217065B2

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