Pyridine N-Oxide → Methyl 3,3-dimethyl-5-oxovalerate

HRID 1290298Notes

Reaction equation

HRID 1290298 reaction equation
Br[CH2:2][CH2:3][C:4]([CH3:11])([CH3:10])[CH2:5][C:6]([O:8][CH3:9])=[O:7].[N+]1([O-:18])C=CC=CC=1.C(=O)(O)[O-].[Na+].C(=O)([O-])[O-].[NH4+].[NH4+]>C1(C)C=CC=CC=1.O>[CH3:10][C:4]([CH3:11])([CH2:3][CH:2]=[O:18])[CH2:5][C:6]([O:8][CH3:9])=[O:7]

Participants

7

Reactant 4

HCID 12753Pyridine N-OxideHCID 516892Sodium BicarbonateHCID 517111Ammonium CarbonateHCID 15276782Methyl 5-bromo-3,3-dimethylpentanoate

Product 1

HCID 3018723Methyl 3,3-dimethyl-5-oxovalerateYield 63%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

A mixture of methyl 5-bromo-3,3-dimethylpentanoate (5.0 g), pyridine-N-oxide (4.49 g), sodium bicarbonate (3.77 g) and toluene (30 cm3) was heated at the reflux temperature with vigorous agitation for a period of 14 hours. After cooling the mixture to the ambient temperature, water (20 cm3), saturated ammonium carbonate solution (20 cm3) and toluene (50 cm3) were added and the aqueous phase separated and extracted with toluene (3×75 cm3). The toluene extracts were added to the main organic phase and the whole dried over anhydrous magnesium sulphate concentrated by evaporation of the more volatile components under reduced pressure. The residual liquid was purified by Kugelrohr distillation (130° C./water pump pressure) to give methyl 3,3-dimethyl-5-oxopentanoate in 63% yield.

Workup

  1. temperaturewas heated at the reflux temperature with vigorous agitation for a period of 14 hours
  2. additionwere added
  3. customthe aqueous phase separated
  4. extractionextracted with toluene (3×75 cm3)
  5. additionThe toluene extracts were added to the main organic phase
  6. dry with materialthe whole dried over anhydrous magnesium sulphate
  7. concentrationconcentrated by evaporation of the more volatile components under reduced pressure
  8. distillationThe residual liquid was purified by Kugelrohr distillation (130° C./water pump pressure)

Sources & evidence

ORD record
ord-9f168e7594f146d59b75304cfdc50861
Source dataset
uspto-grants-1998_05
Patent number
US05750769

Reaction notes

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