Citric Acid → Ethyl 3-oxo-3-(2,3,4-trichlorophenyl)propanoate

HRID 600905Notes

Reaction equation

HRID 600905 reaction equation
[Cl:1][C:2]1[C:10]([Cl:11])=[C:9]([Cl:12])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.C(N1C=CN=C1)(N1C=CN=C1)=O.[K+].[CH2:26]([O:28][C:29](=[O:34])[CH2:30]C([O-])=O)[CH3:27].C(N(CC)CC)C.[Cl-].[Mg+2].[Cl-].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O1CCCC1.C(OCC)(=O)C.CCCCCC>[Cl:1][C:2]1[C:10]([Cl:11])=[C:9]([Cl:12])[CH:8]=[CH:7][C:3]=1[C:4]([CH2:30][C:29]([O:28][CH2:26][CH3:27])=[O:34])=[O:6]

Participants

10

Reactant 6

HCID 311Citric AcidHCID 57832,3,4-Trichlorobenzoic acidHCID 8471TriethylamineHCID 682631,1'-CarbonyldiimidazoleHCID 3446434Potassium ethyl malonateHCID 5360315Magnesium Chloride

Product 1

HCID 53401267Ethyl 3-oxo-3-(2,3,4-trichlorophenyl)propanoateYield 45.4%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

2,3,4-trichlorobenzoic acid (4.51 g, 20.0 mmol) was dissolved in tetrahydrofuran (80 ml), carbonyldiimidazole (3.89 g, 24.0 mmol) was added thereto while cooling with ice, and then stirred at room temperature for 3 hours (solution A). Meanwhile, malonic acid monoethyl ester monopotassium salt (6.81 g, 40.0 mmol) was suspended in ethyl acetate, and while cooling with ice, triethylamine (13.9 ml, 100.0 mmol) and magnesium chloride (5.71 g, 60.0 mmol) were added thereto. After stirring at room temperature for 3 hours, the reaction solution was cooled with ice and the above-described solution A was dripped into this reaction solution over a period of 10 minutes. After then washing solution A into the reaction solution using tetrahydrofuran (10 ml), it was stirred at room temperature for 14 hours, and then the reaction solution was poured into a 10% aqueous citric acid solution (200 ml). This was then extracted with ethyl acetate (200 ml), washed with saturated saline solution (200 ml), and then dried over anhydrous sodium sulfate. After then removing the drying agent by filtration, the solvent was evaporated under a reduced pressure, and the crude product obtained was subject to silica gel chromatography, thereby obtaining 2.681 g (45%) of the title compound as a pale-red oil from an n-hexane:ethyl acetate=5:1 eluate.

Workup

  1. temperaturewhile cooling with ice
  2. additionwere added
  3. temperaturethe reaction solution was cooled with ice
  4. stirringwas stirred at room temperature for 14 hours
  5. extractionThis was then extracted with ethyl acetate (200 ml)
  6. washwashed with saturated saline solution (200 ml)
  7. dry with materialdried over anhydrous sodium sulfate
  8. customAfter then removing the drying agent
  9. filtrationby filtration
  10. customthe solvent was evaporated under a reduced pressure
  11. customthe crude product obtained

Sources & evidence

ORD record
ord-973d659adb8f4f8796789400cac37754
Source dataset
uspto-grants-2011_03
Patent number
US07902226B2

Reaction notes

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