Potassium Carbonate → 4-{(E)-2-[4-(2-tert-butoxycarbonylethyl)-2,6-dichlorophenyl]-vinyl}-3-nitrobenzoic acid methyl ester

HRID 1514961노트

반응식

HRID 1514961 반응식
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10]Br)=[C:6]([N+:12]([O-:14])=[O:13])[CH:5]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:35]([O:39][C:40](=[O:53])[CH2:41][CH2:42][C:43]1[CH:48]=[C:47]([Cl:49])[C:46]([CH:50]=O)=[C:45]([Cl:52])[CH:44]=1)([CH3:38])([CH3:37])[CH3:36].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7](/[CH:10]=[CH:50]/[C:46]2[C:45]([Cl:52])=[CH:44][C:43]([CH2:42][CH2:41][C:40]([O:39][C:35]([CH3:37])([CH3:36])[CH3:38])=[O:53])=[CH:48][C:47]=2[Cl:49])=[C:6]([N+:12]([O-:14])=[O:13])[CH:5]=1

참가 물질

6

반응물 4

HCID 11430Potassium CarbonateHCID 11776TriphenylphosphineHCID 13399987Methyl 4-(bromomethyl)-3-nitrobenzoateHCID 866328253-(3,5-Dichloro-4-formylphenyl)-propionic acid tert-butyl ester

생성물 1

HCID 669652714-{(E)-2-[4-(2-tert-butoxycarbonylethyl)-2,6-dichlorophenyl]-vinyl}-3-nitrobenzoic acid methyl ester

시약·촉매·용매 1

HCID 6228Dimethylformamide용매2회

반응 조건

온도
100 °C

실험 절차

To a solution of 4-bromomethyl-3-nitrobenzoic acid methyl ester (1.64 g, 6.0 mmol) in DMF (15 mL) was added triphenylphosphine (1.57 g, 6.0 mmol) and the mixture was heated at 100° C. for 30 min. To this solution was added a solution of 3-(3,5-dichloro-4-formylphenyl)-propionic acid tert-butyl ester (1.50 g, 4.95 mmol) (from Example 6-25) in DMF (5 mL) in one portion, followed by pulverized potassium carbonate (1.37 g, 9.9 mmol) and the mixture was heated at 100° C. for 18 h. The reaction mixture was partitioned between ethyl acetate and water, washed with brine, dried with MgSO4, filtered, and concentrated. The crude residue was purified by flash chromatography on silica gel, eluting with a gradient of 0-50% ethyl acetate/heptane to obtain 4-{(E)-2-[4-(2-tert-butoxycarbonylethyl)-2,6-dichlorophenyl]-vinyl}-3-nitrobenzoic acid methyl ester as a yellow solid. MS (m/z) 497.1 (M+18); 1H NMR (DMSO-d6, 400 MHz) δ 8.49 (d, J=1.64 Hz, 1H), 8.28 (dd. J=8.15, 1.58 Hz, 1H), 8.14 (d, J=8.21 Hz, 1H), 7.47 (s, 2H), 7.47 (d, J=16.7 Hz, 1H), 7.33 (d, J=16.4 Hz, 1H), 3.93 (s, 3H), 2.83 (t, J=7.33 Hz, 2H), 2.58 (t, J=7.33 Hz, 2H), 1.37 (s, 9H).

후처리

  1. temperaturethe mixture was heated at 100° C. for 18 h
  2. customThe reaction mixture was partitioned between ethyl acetate and water
  3. washwashed with brine
  4. dry with materialdried with MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude residue was purified by flash chromatography on silica gel
  8. washeluting with a gradient of 0-50% ethyl acetate/heptane

출처 및 근거

ORD 기록
ord-d9d0fec612d8463193d06e86926ac3c8
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08222248B2

반응 노트

불러오는 중…