Cesium carbonate → Ethyl 2-(4-(benzyloxy)-2-formylphenoxy)-2-methylpropanoate

HRID 854523노트

반응식

HRID 854523 반응식
[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]([OH:17])=[C:13]([CH:16]=1)[CH:14]=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:19]([CH3:26])([CH3:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21].C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C>[CH2:23]([O:22][C:20](=[O:21])[C:19]([O:17][C:12]1[CH:11]=[CH:10][C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[CH:16][C:13]=1[CH:14]=[O:15])([CH3:26])[CH3:25])[CH3:24]

참가 물질

5

반응물 3

HCID 10796Cesium carbonateHCID 11745Propanoic acid, 2-bromo-2-methyl-, ethyl esterHCID 8783625-(Benzyloxy)-2-hydroxybenzaldehyde

생성물 1

HCID 53421768Ethyl 2-(4-(benzyloxy)-2-formylphenoxy)-2-methylpropanoate수율 89%

시약·촉매·용매 1

HCID 6228Dimethylformamide용매

실험 절차

5-Benzyloxy-2-hydroxy-benzaldehyde (Kappe, T.; Witoszynskyj, T. Arch. Pharm., 1975, 308 (5), 339-346) (2.28 g, 10.0 mmol), ethyl bromoisobutyrate (2.2 mL, 15 mmol), and cesium carbonate (3.26 g, 10.0 mmol) in dry DMF (25 mL) are heated at 80° C. for 18 h. The reaction mixture is cooled and partitioned between water (30 mL) and ether (75 mL). The organic layer is washed with brine (15 mL). The aqueous layers are back-extracted with ethyl acetate (30 mL), and the organic layer is washed with brine (20 mL). The combined organic layers are dried (Na2SO4) and concentrated to a brown oil. The crude product is purified by flash chromatography using hexanes:ethyl acetate (2.5:1) to give a pale yellow solid (3.04 g, 89%): mp 65° C.; 1H NMR (400 MHz, CDCl3) δ 1.24 (t, 3H, J=7.1 Hz), 1.62 (s, 6H), 4.23 (q, 2H, J=7.1 Hz), 6.81 (d, 1H, J=8.8 Hz), 7.10 (dd, 1H, J=4.6, 9.0 Hz), 7.30-7.43 (m, 6H); MS (ES) m/e 343.1 [M+1].

후처리

  1. temperatureThe reaction mixture is cooled
  2. custompartitioned between water (30 mL) and ether (75 mL)
  3. washThe organic layer is washed with brine (15 mL)
  4. extractionThe aqueous layers are back-extracted with ethyl acetate (30 mL)
  5. washthe organic layer is washed with brine (20 mL)
  6. dry with materialThe combined organic layers are dried (Na2SO4)
  7. concentrationconcentrated to a brown oil
  8. customThe crude product is purified by flash chromatography

출처 및 근거

ORD 기록
ord-1e744ee3b26b4d44992a4d5d36729576
출처 데이터셋
uspto-grants-2007_08
특허 번호
US07259175B2

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