Acetic Acid → Methyl 2-(2-cyanobenzylidene)-4,4-dimethoxyacetoacetate

HRID 1759099Notes

Reaction equation

HRID 1759099 reaction equation
[C:1]([C:3]1[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=1[CH:5]=O)#[N:2].[CH3:11][O:12][CH:13]([O:21][CH3:22])[C:14](=[O:20])[CH2:15][C:16]([O:18][CH3:19])=[O:17].C(O)(=O)C.N1CCCCC1>C1C=CC=CC=1>[C:1]([C:3]1[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=1[CH:5]=[C:15]([C:14]([CH:13]([O:12][CH3:11])[O:21][CH3:22])=[O:20])[C:16]([O:18][CH3:19])=[O:17])#[N:2]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 8082PiperidineHCID 1012092-CyanobenzaldehydeHCID 11008445Methyl 4,4-dimethoxy-3-oxobutanoate

Product 1

HCID 53675930Methyl 2-(2-cyanobenzylidene)-4,4-dimethoxyacetoacetateYield 62.6%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent2×

Procedure

To a mixture of 2-cyanobenzaldehyde (5.0 g), methyl 4, 4-dimethoxyacetoacetate (7.39 g) and acetic acid (0.458 g) in benzene (15 ml) was added portionwise each one third of a solution of piperidine (390 mg) in benzene (5 ml) for each 20 minutes' interval. The mixture was heated to reflux for 2 hours and the resulting water was removed off azeotropically during the reaction course. After cooling, the reaction mixture was shaken with a mixture of benzene (50 ml) and water (30 ml), and the organic layer was separated and washed with diluted aqueous sodium bicarbonate solution and water. The aqueous washings were extracted with benzene (30 ml). The benzene extract was combined with the above organic layer, washed with water, dried over magnesium sulfate and evaporated to dryness under reduced pressure. The oily residue (14.8 g) was chromatographed on a column of silica-gel (200 g) and eluted with a mixture of benzene and ethyl acetate (25:1, v/v) to give an oily methyl 2-(2-cyano-benzylidene)-4,4-dimethoxyacetoacetate (6.90 g). The thin layer chromatogram and N.M.R. spectrum of this product show that it consisted of a mixture of two stereoisomers.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 2 hours
  3. customthe resulting water was removed off azeotropically during the reaction course
  4. temperatureAfter cooling
  5. customthe organic layer was separated
  6. washwashed with diluted aqueous sodium bicarbonate solution and water
  7. extractionThe aqueous washings were extracted with benzene (30 ml)
  8. extractionThe benzene extract
  9. washwashed with water
  10. dry with materialdried over magnesium sulfate
  11. customevaporated to dryness under reduced pressure
  12. customThe oily residue (14.8 g) was chromatographed on a column of silica-gel (200 g)
  13. washeluted with a mixture of benzene and ethyl acetate (25:1

Sources & evidence

ORD record
ord-a7149d8379a8495e95c195957d4141c2
Source dataset
uspto-grants-1982_07
Patent number
US04338322

Reaction notes

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