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

HRID 398141ノート

反応式

HRID 398141 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

5-Benzyloxy-2-hydroxy-benzaldehyde (Kappe, T.; Witoszynskj, 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) were heated at 80° C. for 18 h. The reaction mixture was cooled and partitioned between water (30 mL) and ether (75 mL). The organic layer was washed with brine (15 mL). The aqueous layers were back-extracted with ethyl acetate (30 mL), and the organic layer was washed with brine (20 mL). The combined organic layers were dried (Na2SO4) and concentrated to a brown oil. The crude product was 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) δ1.24 (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].

後処理

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

出典と根拠

ORDレコード
ord-f89b4c475e7447b096583d9a9965f9e6
出典データセット
uspto-grants-2003_08
特許番号
US06610696B2

反応ノート

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