Phosphorus oxychloride → Ethyl 3-(4-t-Butylphenyl)-3-chloro-2-ethoxycarbonyl-acrylate

HRID 1740072Notes

Reaction equation

HRID 1740072 reaction equation
[C:1]([C:5]1[CH:23]=[CH:22][C:8]([C:9]([CH:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])=O)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].P(Cl)(Cl)([Cl:26])=O.C(N(C(C)C)CC)(C)C>>[C:1]([C:5]1[CH:23]=[CH:22][C:8]([C:9]([Cl:26])=[C:11]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 81531DiisopropylethylamineHCID 21837646Diethyl 4-t-Butyl-benzoylmalonate

Product 1

HCID 21837650Ethyl 3-(4-t-Butylphenyl)-3-chloro-2-ethoxycarbonyl-acrylateYield 95.5%

Conditions

Temperature
100 °C

Procedure

To a mixture of 72.5 g of diethyl 4-t-butyl-benzoylmalonate and 337.7 g of phosphorus oxychloride, 48.9 g of diisopropylethylamine was added, and the resulting mixture was stirred at 100° C. for 3 hours. The reaction mixture was evaporated under reduced pressure, and the resulting solid residue was extracted with diethyl ether, and the still remaining solid was mixed with water and then extracted diethyl ether. The extracts were combined, concentrated under reduced pressure, washed with 1N hydrochloric acid, 1N aqueous sodium hydroxide and water successively and dried over anhydrous sodium sulfate. The insoluble were filtered off, and the solvent was removed by evaporation. The resulting residue was purified by silica gel chromatography (eluent; n-hexane/ethyl acetate=7:1) to give 73.19 g of the title compound as a yellow oily substance.

Workup

  1. additionwas added
  2. customThe reaction mixture was evaporated under reduced pressure
  3. extractionthe resulting solid residue was extracted with diethyl ether
  4. additionwas mixed with water
  5. concentrationconcentrated under reduced pressure
  6. washwashed with 1N hydrochloric acid, 1N aqueous sodium hydroxide and water successively
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationThe insoluble were filtered off
  9. customthe solvent was removed by evaporation
  10. customThe resulting residue was purified by silica gel chromatography (eluent; n-hexane/ethyl acetate=7:1)

Sources & evidence

ORD record
ord-c7974a2ffdc54bba81e3eb5d02714088
Source dataset
uspto-grants-1999_10
Patent number
US05968967

Reaction notes

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