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

HRID 847066Notes

Reaction equation

HRID 847066 reaction equation
[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

Participants

5

Reactant 4

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

Product 1

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

Procedure

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) δ7.81 (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.

Workup

  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

Sources & evidence

ORD record
ord-499effcc12d842abbf7dda768b56687f
Source dataset
uspto-grants-1992_08
Patent number
US05138069

Reaction notes

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