Methyl iodide → Dimethyl 2-methyl-2-(4-nitrophenyl)malonate

HRID 1842969Notes

Reaction equation

HRID 1842969 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([CH:10]([C:15]([O:17][CH3:18])=[O:16])[C:11]([O:13][CH3:14])=[O:12])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:19]([O-])([O-])=O.[K+].[K+].CI>CN(C=O)C>[CH3:19][C:10]([C:7]1[CH:8]=[CH:9][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)([C:15]([O:17][CH3:18])=[O:16])[C:11]([O:13][CH3:14])=[O:12]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 2764303Dimethyl 2-(4-nitrophenyl)malonate

Product 1

HCID 1485451Dimethyl 2-methyl-2-(4-nitrophenyl)malonateYield 66.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of dimethyl 2-(4-nitrophenyl)malonate (10 g, 39.52 mmol, 1.0 eq) and K2CO3 (10.9 g 79.05 mmol 2.0 eq) in DMF (40 mL), was added methyl iodide (4.94 mL, 79.05 mmol 2.0 eq) at 0° C. and the mixture stirred at RT for 18 h. K2CO3 was filtered out and the filtrate concentrated under vacuum. The residue was diluted with water (80 mL) and extracted with EtOAc (2×80 mL). The organic layer was separated washed with brine solution, dried over anhydrous Na2SO4 and the solvent evaporated to get dimethyl 2-methyl-2-(4-nitrophenyl)malonate (7 g, 66%; TLC system: EtOAc/PE (3:7), Rf: 0.5.)

Workup

  1. filtrationK2CO3 was filtered out
  2. concentrationthe filtrate concentrated under vacuum
  3. additionThe residue was diluted with water (80 mL)
  4. extractionextracted with EtOAc (2×80 mL)
  5. customThe organic layer was separated
  6. washwashed with brine solution
  7. dry with materialdried over anhydrous Na2SO4
  8. customthe solvent evaporated

Sources & evidence

ORD record
ord-0ac5f0688225410bafab0b1d96e24146
Source dataset
uspto-grants-2015_02
Patent number
US08946204B2

Reaction notes

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