Water → Dimethyl 2-(4-bromobenzyl)malonate

HRID 931509Notes

Reaction equation

HRID 931509 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].C(=O)([O-])[O-].[K+].[K+].[Br:16][C:17]1[CH:22]=[CH:21][C:20]([CH2:23]Br)=[CH:19][CH:18]=1.O>CN(C)C=O>[Br:16][C:17]1[CH:22]=[CH:21][C:20]([CH2:23][CH:2]([C:1]([O:8][CH3:9])=[O:7])[C:3]([O:5][CH3:6])=[O:4])=[CH:19][CH:18]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7943Dimethyl malonateHCID 11430Potassium CarbonateHCID 685274-Bromobenzyl bromide

Product 1

HCID 2801290Dimethyl 2-(4-bromobenzyl)malonateYield 91%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
50 °C

Procedure

A mixture of dimethyl malonate (42.6 g, 322.73 mmol, 4.00 equiv) and potassium carbonate (22.3 g, 161.59 mmol, 2.00 equiv) in N,N-dimethylformamide (200 mL) was stirred for 30 min at 50° C. A solution of 1-bromo-4-(bromomethyl)benzene (20 g, 80.65 mmol, 1.00 equiv) in N,N-dimethylformamide (80 mL) was then added dropwise with stirring to the reaction mixture. The resulting solution was stirred at 50° C. for 2 h. Water (100 mL) was added and the mixture was extracted with 1×400 mL of ethyl acetate. The organic layer was washed with 2×100 mL of brine, dried over anhydrous sodium sulfate and concentrated under vacuum to give 22 g (91%) of dimethyl 2-(4-bromobenzyl)malonate as a white solid. LC-MS: (ES, m/z): 301 [M+H]+, 126, 120.

Workup

  1. stirringwith stirring to the reaction mixture
  2. stirringThe resulting solution was stirred at 50° C. for 2 h
  3. extractionthe mixture was extracted with 1×400 mL of ethyl acetate
  4. washThe organic layer was washed with 2×100 mL of brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-070dcded0d354048b96ab1095887cde8
Source dataset
uspto-grants-2016_03
Patent number
US09296732B2

Reaction notes

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