Propanal → HCID 53856792, compound

HRID 129980Notes

Reaction equation

HRID 129980 reaction equation
[CH:1]([O:3][CH3:4])=[O:2].C[O-].[Na+].CO.[CH:10](=[O:13])[CH2:11][CH3:12].Br[CH2:15][CH2:16][CH3:17]>C1C=CC=CC=1>[CH3:12][CH:11]([CH:4]=[O:3])[CH:10]=[O:13].[CH3:12][C:11](=[CH:1][O:2][CH2:15][CH2:16][CH3:17])[CH:10]=[O:13]

Participants

7

Reactant 4

HCID 527PropanalHCID 78401-BromopropaneHCID 7865Methyl formate2×HCID 23694274Sodium methanolate methanol

Product 2

HCID 98735MethylmalondialdehydeHCID 53856792HCID 53856792, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

The sodium enolate of methylmalonaldehyde was prepared using methyl formate, sodium methoxide/methanol solution, and propionaldehyde exactly as described by the procedure of Example I. After addition of 5 mL of benzene to this mixture, excess methyl formate was removed by fractional distillation in accordance with Example II. Once the formate ester had been removed, 4.0 mL of N,N-dimethylformamide (spectrophotometric grade) was added to the mixture and distillative removal of methyl alcohol and most of the benzene was accomplished as outlined in the procedure of Example II. After allowing the mixture of the sodium enolate of methylmalonaldehyde in DMF to cool to room temperature, 1.00 mL (11.0 mmoles) of 1-bromopropane (purchased from Aldrich Chemical Co., Milwaukee, Wisc.) was added. This mixture was then stirred at 62° C. (oil bath temperature), while being maintained under a nitrogen atmosphere, for 18 hours. Isolation of the product as described in the procedure of Example II, followed by evaporative distillation, afforded 350 mg (82% yield) of 2-methyl-3-propoxypropenal: boiling point 60°-68° C. (bath temperature, 0.25 mm). The proton NMR spectrum of this vinylogous ester exhibited a singlet at δ9.15 (CHO), a quartet (J=1.5 Hz) at δ6.94 (vinyl H), a triplet (J=6.5 Hz) at δ4.1 (CH2O), a doublet (J=1.5 Hz) at δ1.72 (vinyl CH3), and a triplet (J=7 Hz) at δ1.02 (CH3CH2).

Workup

  1. customwas removed by fractional distillation in accordance with Example II
  2. customOnce the formate ester had been removed
  3. addition4.0 mL of N,N-dimethylformamide (spectrophotometric grade) was added to the mixture and distillative removal of methyl alcohol and most of the benzene
  4. additionthe mixture of the sodium enolate of methylmalonaldehyde in DMF
  5. temperaturewhile being maintained under a nitrogen atmosphere, for 18 hours
  6. distillationfollowed by evaporative distillation

Sources & evidence

ORD record
ord-a0c589e958fd49349ad363ac51cf28ea
Source dataset
uspto-grants-1995_11
Patent number
US05471005

Reaction notes

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