Bromomethyl 4-methoxyphenyl ketone → Diethyl alpha-(4-methoxyphenacyl)malonate

HRID 856854Notes

Reaction equation

HRID 856854 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].CC(C)([O-])C.[K+].[CH3:18][O:19][C:20]1[CH:29]=[CH:28][C:23]([C:24](=[O:27])[CH2:25]Br)=[CH:22][CH:21]=1.[Cl-].[NH4+]>O1CCCC1>[CH3:18][O:19][C:20]1[CH:29]=[CH:28][C:23]([C:24](=[O:27])[CH2:25][CH:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])=[CH:22][CH:21]=1

Participants

6

Reactant 4

HCID 4965Bromomethyl 4-methoxyphenyl ketoneHCID 7761Diethyl MalonateHCID 25517Ammonium ChlorideHCID 23665647Potassium tert-butoxide

Product 1

HCID 21862838Diethyl alpha-(4-methoxyphenacyl)malonateYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

3.50 g (21.8 mmol) of diethyl malonate were dissolved in 60 ml of anhydrous tetrahydrofuran, and 2.70 g (24.0 mmol) of potassium t-butoxide were added to the resulting solution, whilst ice-cooling. The mixture was then stirred for 1 hour. At the end of this time, a solution of 5.00 g (21.8 mmol) of 4-methoxyphenacyl bromide in 40 ml of anhydrous tetrahydrofuran was slowly added dropwise to the mixture, whilst ice-cooling. The mixture was stirred, whilst ice-cooling for 1 hour, and then a saturated aqueous solution of ammonium chloride was added, and the mixture was extracted with ethyl acetate. The organic extract was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was removed by distillation under reduced pressure. The residue thus obtained was applied to a silica gel chromatography column and eluted with a 1:4 by volume mixture of ethyl acetate and hexane, to give 4.87 g of the title compound as a slightly yellow oily substance (yield 73%).

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. stirringThe mixture was stirred, whilst ice-
  4. temperaturecooling for 1 hour
  5. extractionthe mixture was extracted with ethyl acetate
  6. extractionThe organic extract
  7. washwas washed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customthe solvent was removed by distillation under reduced pressure
  10. customThe residue thus obtained
  11. washeluted with a 1:4 by volume mixture of ethyl acetate and hexane

Sources & evidence

ORD record
ord-447563d0f8b44b8f9a0ba39086496646
Source dataset
uspto-grants-2006_12
Patent number
USRE039420E1

Reaction notes

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