Sodium Iodide → Ethyl 3-(4-methylphenyl)-3-oxo-2-(allyl)propanoate

HRID 466420ノート

反応式

HRID 466420 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:4][CH:3]=1.[O-]CC.[Na+].[CH2:20](Br)[CH:21]=[CH2:22].[I-].[Na+]>>[CH3:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](=[O:15])[CH:9]([CH2:22][CH:21]=[CH2:20])[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:6][CH:7]=1

参加物

5

反応物 4

HCID 5238Sodium IodideHCID 7841Allyl bromideHCID 292637Ethyl 3-(4-methylphenyl)-3-oxopropanoateHCID 2723922Sodium ethoxide

生成物 1

HCID 15698113Ethyl 3-(4-methylphenyl)-3-oxo-2-(allyl)propanoate収率 97.5%

実験手順

Ethyl 3-(4-methylphenyl)-3-oxopropanoate (prepared as described in W. Wierenga and H. I. Skulnick, J. Org. Chem. (1979), 44, 310) (63.66 g, 309 mmol, 1 eq) was added to a freshly prepared sodium ethoxide solution (Na, 7.43 g, 323 mmol, 1.05 eq; EtOH, 250 mL). The ethanol was removed in vacuo and the residue was dissolved in DMF (250 mL). Allyl bromide (29.3 mL, 338 mmol, 1.1 eq) followed by sodium iodide (4.56 g, 304 mmol, 1 eq) were then added and the contents stirred overnight at room temperature. The DMF was removed in vacuo, water (250 mL) was added and the aqueous layer extracted with ethyl acetate (3×200 mL). The organic layers were dried (MgSO4) and the solvent removed in vacuo to yield 74.21 g of an amber oil. NMR (200 MHz, CDCl3) δ 7.81 (d, 2H, J=10 Hz); 7.30 (d, 2H, J=10 Hz); 5.96-5.72 (m, 1H); 5.21-5.00 (m, 2H); 4.41 (t, 1H, J=7 Hz); 4.16 (q, 2H, J=7 Hz); 2.78 (t, 2H, J=7 Hz); 2.42 (s, 3H); 1.18 (t, 3H, J=7 Hz). Anal. Calcd. for C15H18O3 : C, 73.15; H, 7.37. Found: C, 73.10; H, 7.38.

後処理

  1. customThe ethanol was removed in vacuo
  2. dissolutionthe residue was dissolved in DMF (250 mL)
  3. additionwere then added
  4. customThe DMF was removed in vacuo, water (250 mL)
  5. additionwas added
  6. extractionthe aqueous layer extracted with ethyl acetate (3×200 mL)
  7. dry with materialThe organic layers were dried (MgSO4)
  8. customthe solvent removed in vacuo

出典と根拠

ORDレコード
ord-58c2283e7bc24845bb7e8f881992aae1
出典データセット
uspto-grants-1992_10
特許番号
US05155118

反応ノート

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