Benzaldehyde → Ethyl cinnamoylacetate

HRID 1906025Notes

Reaction equation

HRID 1906025 reaction equation
[C:1]([O:7][CH2:8][CH3:9])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].C(N(CC)CC)C.[CH:17](=O)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.O>C(Cl)(Cl)(Cl)Cl.O1CCCC1.[Ti](Cl)(Cl)(Cl)Cl>[O:4]=[C:3]([CH:5]=[CH:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[CH2:2][C:1]([O:7][CH2:8][CH3:9])=[O:6]

Participants

8

Reactant 4

HCID 240BenzaldehydeHCID 962WaterHCID 8471TriethylamineHCID 8868Ethyl Acetoacetate

Product 1

HCID 54004396Ethyl cinnamoylacetateYield 75.3%

Reagents, catalysts & solvents 3

HCID 24193Titanium TetrachlorideCatalystHCID 5943Carbon TetrachlorideSolventHCID 8028TetrahydrofuranSolvent4×

Procedure

A solution of 6.6 ml (0.06 moles) of titanium tetrachloride in 30 ml of carbon tetrachloride was added dropwise with rapid stirring to 300 ml of cold (-50° ) tetrahydrofuran. The mixture was allowed to warm to 0° and a solution of 5.85 g (0.045 moles) of ethyl acetoacetate in 50 ml of tetrahydrofuran was added dropwise over about 20 minutes. After the mixture was stirred an additional 30 minutes, a solution of 25.2 ml (0.180 moles) of triethylamine in 50 ml of tetrahydrofuran was added dropwise over 45 minutes. After the mixture was stirred an additional 45 minutes, a solution of 4.8 g (0.045 moles) of benzaldehyde in 50 ml of tetrahydrofuran was added dropwise over 30 minutes. The reaction mixture was allowed to warm to room temperature and then stirred for 24 hours. Water (50 ml) was added and the resultant two-phase mixture was stirred for two hours. After the layers were separated, the aqueous layer was extracted with 50 ml of ethyl acetate. The ethyl acetate extract was combined with the initially separated organic layer, dried over sodium sulfate, filtered, and concentrated in vacuo to 9.8 g of an oil. Chromatography on silica gel gave 7.4 g of the title compound as a solid, m.p. ca. 49°. Structure assignment was supported by nmr and infrared spectra and by elemental analysis.

Workup

  1. temperatureto warm to 0°
  2. stirringAfter the mixture was stirred an additional 45 minutes
  3. stirringstirred for 24 hours
  4. customAfter the layers were separated
  5. extractionthe aqueous layer was extracted with 50 ml of ethyl acetate
  6. extractionThe ethyl acetate extract
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo to 9.8 g of an oil

Sources & evidence

ORD record
ord-3a60cfcd09104a40a37316dd49f2b065
Source dataset
uspto-grants-1987_03
Patent number
US04649157

Reaction notes

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