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Diethyl Malonate → Ethyl 3-(2,4-dimethoxyphenyl)-2-ethoxycarbonyl-2-propenoate

HRID 1418169
Notes
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Reaction equation

HRID 1418169 reaction equation
[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH:5]=O.[C:13]([O:21][CH2:22][CH3:23])(=[O:20])[CH2:14][C:15]([O:17][CH2:18][CH3:19])=[O:16]>C1C=CC=CC=1.C(OCC)(=O)C.CCCCCC.C(O)(=O)C1C=CC=CC=1.N1CCCCC1>[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:4]=1[CH:5]=[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:13]([O:21][CH2:22][CH3:23])=[O:20]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 2

HCID 7761Diethyl MalonateHCID 691752,4-Dimethoxybenzaldehyde

Product 1

HCID 10757178Ethyl 3-(2,4-dimethoxyphenyl)-2-ethoxycarbonyl-2-propenoateYield 92.1%

Reagents, catalysts & solvents 5

HCID 243Benzoic AcidCatalystHCID 8082PiperidineCatalyst
HCID 241
Benzene
Solvent
HCID 8058HexaneSolvent
HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 10.0 g (60.2 mmol) of 2,4-dimethoxybenzaldehyde, 10.6 g (66.3 mmol) of diethyl malonate, 0.19 g (1.6 mmol) of benzoic acid and 0.20 ml (2.0 mmol) of piperidine in 43 ml of benzene was heated under reflux for 16 hours, whilst removing the water formed. At the end of this time, it was allowed to cool to room temperature, and then the reaction mixture was diluted with a 2:1 by volume mixture of ethyl acetate and hexane, and the diluted solution was washed with a saturated aqueous solution of sodium hydrogencarbonate, with 1N aqueous hydrochloric acid, with water and with a saturated aqueous solution of sodium chloride, in that order, after which it was dried. The solvent was removed by distillation under reduced pressure, and the resulting residue was recrystallized from a mixture of diisopropyl ether and hexane, to give 17.1 g (yield 92%) of the title compound as crystals, melting at 40°-41° C. (from a mixture of diisopropyl ether and hexane).

Workup

  1. temperatureunder reflux for 16 hours
  2. customwhilst removing the water
  3. customformed
  4. washthe diluted solution was washed with a saturated aqueous solution of sodium hydrogencarbonate, with 1N aqueous hydrochloric acid, with water and with a saturated aqueous solution of sodium chloride, in that order
  5. customafter which it was dried
  6. customThe solvent was removed by distillation under reduced pressure
  7. customthe resulting residue was recrystallized from a mixture of diisopropyl ether and hexane

Sources & evidence

ORD record
ord-ff35cc4490604c2bb0adaa27dd219b4c
Source dataset
uspto-grants-1999_03
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05880147

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes