Diethyl Carbonate → Diethyl 4-bromophenylmalonate

HRID 1796362Notes

Reaction equation

HRID 1796362 reaction equation
[C:1](=[O:8])([O:5][CH2:6][CH3:7])OCC.[H-].[Na+].[Br:11][C:12]1[CH:17]=[CH:16][C:15]([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:14][CH:13]=1>C1C=CC=CC=1>[Br:11][C:12]1[CH:13]=[CH:14][C:15]([CH:18]([C:1]([O:5][CH2:6][CH3:7])=[O:8])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:16][CH:17]=1

Participants

5

Reactant 3

HCID 7766Diethyl CarbonateHCID 24758Sodium hydrideHCID 7020609Ethyl 2-(4-bromophenyl)acetate

Product 1

HCID 10519382Diethyl 4-bromophenylmalonateYield 89.2%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

Under argon flow, 10.85 g of diethyl carbonate was dissolved in 60 ml of benzene, and 2.75 g of 60% sodium hydride was added and the mixture was heated to reflux. A solution of 5.58 g of ethyl 4-bromophenylacetate/20 ml of benzene was added dropwise to the solution over 1 hour, and the mixture was heated to reflux for 1 hour. After cooling, ice-cold water was added dropwise to the reaction solution slowly. The organic layer was separated, washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was purified by silica gel column chromatography (Wakogel® C-200, n-hexane:ethyl acetate=10:1) to provide 6.45 g of the objective compound as colorless oil.

Workup

  1. temperaturethe mixture was heated to reflux
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 1 hour
  4. temperatureAfter cooling
  5. additionice-cold water was added dropwise to the reaction solution slowly
  6. customThe organic layer was separated
  7. washwashed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel column chromatography (Wakogel® C-200, n-hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-377e67cd08dd4d46991b45835471e253
Source dataset
uspto-grants-2006_04
Patent number
US07030143B2

Reaction notes

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