4-Nitrobenzyl bromide → Diethyl 2-(4-nitrobenzyl)-2-methylmalonate

HRID 2176909Notes

Reaction equation

HRID 2176909 reaction equation
C[CH2:2][CH:3]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:4]([O:6][CH3:7])=[O:5].[O-][CH2:14]C.[Na+].[Na].[N+:18]([C:21]1[CH:28]=[CH:27][C:24]([CH2:25]Br)=[CH:23][CH:22]=1)([O-:20])=[O:19]>CCO>[N+:18]([C:21]1[CH:28]=[CH:27][C:24]([CH2:25][C:3]([CH3:2])([C:4]([O:6][CH2:7][CH3:14])=[O:5])[C:8]([O:10][CH2:11][CH3:12])=[O:9])=[CH:23][CH:22]=1)([O-:20])=[O:19]

Participants

6

Reactant 4

HCID 660114-Nitrobenzyl bromideHCID 2723922Sodium ethoxideHCID 5088009HCID 5088009, compoundHCID 5360545Sodium

Product 1

HCID 54496963Diethyl 2-(4-nitrobenzyl)-2-methylmalonateYield 29.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Diethyl methyl malonate (1.60 ml, 9.25 mmol) was added to a freshly prepared solution of sodium ethoxide solution [(sodium (212 mg, 9.25 mmol) in EtOH (20 ml)] and stirred for 1 h. 4-Nitrobenzyl bromide (2.00 g, 9.25 mmol) was added dropwise to the reaction mixture and stirred for 6 h at reflux. The reaction mixture was cooled to room temperature and concentrated. The residue was partitioned between water and CHCl3. The separated organic layer was washed with water, brine solution, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to give the crude product. This was purified by column chromatography over silica gel (100-200 mesh) using 5% ethyl acetate in petroleum ether as eluent to afford 850 mg (29.7%) of diethyl 2-(4-nitrobenzyl)-2-methylmalonate as oily liquid.

Workup

  1. stirringstirred for 6 h
  2. temperatureat reflux
  3. concentrationconcentrated
  4. customThe residue was partitioned between water and CHCl3
  5. washThe separated organic layer was washed with water, brine solution
  6. dry with materialdried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give the crude product
  10. customThis was purified by column chromatography over silica gel (100-200 mesh)

Sources & evidence

ORD record
ord-f8188fccd9b744dba58d28e814b8cad1
Source dataset
uspto-grants-2015_06
Patent number
US09067888B2

Reaction notes

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