Pinacolone → Ethyl pivaloylacetate

HRID 1063799Notes

Reaction equation

HRID 1063799 reaction equation
[Na].C(O[C:5](=O)[C:6]([O:8][CH2:9][CH3:10])=[O:7])C.[C:12]([C:16](C)=[O:17])([CH3:15])([CH3:14])[CH3:13]>C(O)C>[CH2:9]([O:8][C:6](=[O:7])[CH2:5][C:16](=[O:17])[C:12]([CH3:15])([CH3:14])[CH3:13])[CH3:10]

Participants

5

Reactant 3

HCID 6416PinacoloneHCID 7268Diethyl OxalateHCID 5360545Sodium

Product 1

HCID 86950Ethyl pivaloylacetateYield 106.5%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
60 °C

Procedure

Sodium pellets (4.6 g, 200 mmol) were dissolved in ethanol (165 ml) under nitrogen at room temperature and a solution of diethyloxalate (27.2 ml, 200 mmol) in tert-butyl-methyl ketone (20.1 g, 200 mmol) was added dropwise at room temperature over 15 minutes. The reaction was diluted with ethanol (100 ml), heated to 60° C. and stirred at this temperature for 2 hours. After cooling to room temperature the reaction was stirred for 64 hours, poured onto ice-cold 2N HCl (200 ml) and extracted with diethylether (3×200 ml). The combined organic extracts were washed with water, dried over MgSO4 and concentrated under reduced pressure to give 4,4-dimethyl-3-oxo-pentanoic acid ethyl ester (36.7 g) as a yellow oil. 1H NMR (400 MHz, CDCl3): δ=6.48 (1H, s), 4.26-4.37 (2H, quart), 1.29-1.38 (3H, t), 1.17 (9H, s) ppm. LRMS (electrospray): m/z [M+Na]+ 223, [M−H]+ 199.

Workup

  1. temperatureAfter cooling to room temperature the reaction
  2. stirringwas stirred for 64 hours
  3. additionpoured onto ice-cold 2N HCl (200 ml)
  4. extractionextracted with diethylether (3×200 ml)
  5. washThe combined organic extracts were washed with water
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-1c2c54688a5348afa95f980d81a0df49
Source dataset
uspto-grants-2005_11
Patent number
US06967204B2

Reaction notes

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