Diethyl methylmalonate → HCID 21692454, compound

HRID 1463760Notes

Reaction equation

HRID 1463760 reaction equation
[Na].[CH2:2]([O:4][C:5](=[O:13])[CH:6]([CH3:12])[C:7]([O:9][CH2:10]C)=[O:8])C.C[O-].[Na+].[N+:17]([C:20]1[CH:27]=[CH:26][C:23]([CH2:24]Br)=[CH:22][CH:21]=1)([O-:19])=[O:18]>CO>[CH3:2][O:4][C:5](=[O:13])[C:6]([CH3:12])([CH2:24][C:23]1[CH:26]=[CH:27][C:20]([N+:17]([O-:19])=[O:18])=[CH:21][CH:22]=1)[C:7]([O:9][CH3:10])=[O:8]

Participants

6

Reactant 4

HCID 11857Diethyl methylmalonateHCID 660114-Nitrobenzyl bromideHCID 5360545Sodium2×HCID 10942334Sodium Methoxide

Product 1

HCID 21692454HCID 21692454, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

11.5 g (0.5 mol) of sodium in a stream of nitrogen was placed in a dry 1000 ml three-necked flask with a reflux condenser, a drying tube and a dropping funnel with pressure compensation. Next, 350 ml of methanol was carefully added dropwise and agitated until the sodium had completely dissolved. A methanolic solution of 87 g (0.5 mol) methylmalonic acid diethyl ester was added very slowly dropwise to the sodium methanolate solution, which was still warm. At the end of the addition, the mixture was stirred for a further 30 minutes, after which 4-nitrobenzyl bromide was added in portions, using a powder funnel. After everything had dissolved, the mixture was first reflux-heated for two hours and then agitated at room temperature overnight. The solvent was removed in a rotary evaporator and water was added to the residue, which was repeatedly extracted with ethyl acetate (250 ml portions). The combined organic extracts were washed with saturated common salt solution and dried over sodium sulphate. After removing the solvent, faintly yellow crystals were left. Recrystallisation was from dimethyl formamide (DMF) and water.

Workup

  1. dissolutionhad completely dissolved
  2. temperaturewas still warm
  3. additionAt the end of the addition
  4. dissolutionAfter everything had dissolved
  5. temperaturethe mixture was first reflux-heated for two hours
  6. stirringagitated at room temperature overnight
  7. customThe solvent was removed in a rotary evaporator and water
  8. additionwas added to the residue, which
  9. extractionwas repeatedly extracted with ethyl acetate (250 ml portions)
  10. washThe combined organic extracts were washed with saturated common salt solution
  11. dry with materialdried over sodium sulphate
  12. customAfter removing the solvent, faintly yellow crystals
  13. waitwere left
  14. customRecrystallisation

Sources & evidence

ORD record
ord-d6bcc6bda835437687a6a809824335e9
Source dataset
uspto-grants-1994_04
Patent number
US05302370

Reaction notes

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