Benzaldehyde → Diethyl (phenylmethylene)malonate

HRID 1285513Notes

Reaction equation

HRID 1285513 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[CH:12](=O)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.N1CCCCC1.O>C1C=CC=CC=1.C(O)(=O)C1C=CC=CC=1>[CH:12](=[C:2]([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:1]([O:9][CH2:10][CH3:11])=[O:8])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 240BenzaldehydeHCID 962WaterHCID 7761Diethyl MalonateHCID 8082Piperidine

Product 1

HCID 94751Diethyl (phenylmethylene)malonateYield 88%

Reagents, catalysts & solvents 2

HCID 243Benzoic AcidCatalystHCID 241BenzeneSolvent

Procedure

A mixture containing 3.0 mL (19.8 mmoles) of diethyl malonate, 2.0 mL (19.6 mmoles) of benzaldehyde, 0.10 mL of piperidine, and 65 mg of benzoic acid in 35 mL of benzene was heated at reflux for 6 hours with continuous azeotropic removal of water by means of a Dean-Stark trap. Isolation of the product in the manner described in the procedure of Example I, followed by fractional distillation, afforded 4.27 g (88% yield) of diester 8: bp 105°-140° C. (bath temperature, 0.10 mm). Subsequent treatment of diester 8 with 2-nitropropane and sodium ethoxide in ethanol at reflux, as described for the corresponding cyanoester 1 in Example VIII, failed to yield a cyclopropanoid product.

Workup

  1. temperaturewas heated
  2. distillationfollowed by fractional distillation

Sources & evidence

ORD record
ord-eb231cae99454a538acd7d5ec18549b6
Source dataset
uspto-grants-1986_01
Patent number
US04567265

Reaction notes

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