Pyridine → Ethyl 4,4-dimethyl-3-oxo-5-phenylpentanoate

HRID 1504277Notes

Reaction equation

HRID 1504277 reaction equation
O=C(C)[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[Cl-].[Mg+2].[Cl-].N1C=CC=CC=1.[CH3:19][C:20]([CH3:31])([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:21](Cl)=[O:22]>C(Cl)Cl>[CH3:19][C:20]([CH3:31])([CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[C:21](=[O:22])[CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

6

Reactant 4

HCID 1049PyridineHCID 8868Ethyl AcetoacetateHCID 5360315Magnesium ChlorideHCID 133072292,2-Dimethyl-3-phenylpropanoyl chloride

Product 1

HCID 86697460Ethyl 4,4-dimethyl-3-oxo-5-phenylpentanoateYield 18%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Ethyl 3-oxobutanoate (1.09 g, 8.3 mmol) in methylene chloride (16 mL) was mixed with anhydrous magnesium chloride (158 mg, 1.66 mmol), and the reaction solution was cooled to 0° C. and mixed with pyridine (1.34 mL, 16.6 mmol), stirred for 30 minutes, then mixed with 2,2-dimethyl-3-phenylpropanoyl chloride (1.64 g, 8.3 mmol) and stirred for another 30 minutes at the same temperature. The reaction solution was warmed to room temperature and stirred for 20 hours. The methylene chloride was distilled off under reduced pressure, and the residue was with ethanol (2 mL) and at room temperature for 2 days and with toluene (2 mL) at 60° C. for 5 hours. After completion of the reaction, the reaction solution was washed with saturated aqueous sodium hydrogen carbonate and extracted with ethyl acetate (50 mL×2). The solvent was removed from the resulting organic layer under reduced pressure, and the resulting brown oil was purified by intermediate pressure silica gel column chromatography (silica gel 12 g, ethyl acetate:hexane=1:19 to 1:9) to give 370 mg of the desired product as a light brown oil.

Workup

  1. stirringstirred for another 30 minutes at the same temperature
  2. temperatureThe reaction solution was warmed to room temperature
  3. stirringstirred for 20 hours
  4. distillationThe methylene chloride was distilled off under reduced pressure
  5. waitthe residue was with ethanol (2 mL) and at room temperature for 2 days and with toluene (2 mL) at 60° C. for 5 hours
  6. customAfter completion of the reaction
  7. washthe reaction solution was washed with saturated aqueous sodium hydrogen carbonate
  8. extractionextracted with ethyl acetate (50 mL×2)
  9. customThe solvent was removed from the resulting organic layer under reduced pressure
  10. customthe resulting brown oil was purified by intermediate pressure silica gel column chromatography (silica gel 12 g, ethyl acetate:hexane=1:19 to 1:9)

Sources & evidence

ORD record
ord-613d1433596d455aa59e205c17b15572
Source dataset
uspto-grants-2015_12
Patent number
US09212348B2

Reaction notes

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