Diethyl allylmalonate → 2-Allyl-3-methylsuccinic acid

HRID 1074592Notes

Reaction equation

HRID 1074592 reaction equation
C([O:3][C:4](=[O:14])[CH:5]([CH2:11][CH:12]=[CH2:13])C(OCC)=O)C.C([O:17][C:18](=[O:22])[CH:19](Br)[CH3:20])C>COCCOCCOC>[CH2:11]([CH:5]([CH:19]([CH3:20])[C:18]([OH:17])=[O:22])[C:4]([OH:14])=[O:3])[CH:12]=[CH2:13]

Participants

4

Reactant 2

HCID 74900Diethyl allylmalonateHCID 79040Ethyl 2-bromopropionate

Product 1

HCID 199806952-Allyl-3-methylsuccinic acidYield 96%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Procedure

90.5 g (0.5 moles) of 2-allylmalonic acid diethyl ester are reacted in diethylene glycol dimethyl ether with 0.5 moles of alcohol-free sodium ethoxide. 0.5 moles of 2-bromopropionic acid ethyl ester is added dropwise to this solution, with stirring. The mixture is heated for a further 2 hours under reflux and the solvent is then removed. The residue is subsequently subjected to hydrolysis in alcoholic KOH. After drying the organic layer that has separated, it is fractionated. The desired 2-allyl-1-methylethane-tricarboxylic acid 1,2,2-triethyl ester boils under 0.02 torr at 92° to 95° C. The ester is hydrolyzed in alcoholic KOH and, after working up in the customary manner, is decarboxylated at 170° C. with water being split off. The anhydride of 2-allyl-3-methylsuccinic acid (b.p. at 0.1 torr: 108° to 110° C.) is obtained in a 96% yield (based on the ester).

Workup

  1. temperatureThe mixture is heated for a further 2 hours
  2. temperatureunder reflux
  3. customthe solvent is then removed
  4. customThe residue is subsequently subjected to hydrolysis in alcoholic KOH
  5. customAfter drying the organic layer that
  6. customhas separated
  7. customboils under 0.02 torr at 92° to 95° C
  8. customis decarboxylated at 170° C. with water being
  9. customsplit off

Sources & evidence

ORD record
ord-2e09f620998b4121b9648bda659f5ebe
Source dataset
uspto-grants-1983_07
Patent number
US04393220

Reaction notes

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