Diethyl 2-(ethoxymethylidene)-3-oxobutanedioate → HCID 18937855, compound

HRID 1734498Notes

Reaction equation

HRID 1734498 reaction equation
C(O[CH:4]=[C:5]([C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])=O)[C:6]([O:8][CH2:9][CH3:10])=[O:7])C.[N+:18]([CH2:21][C:22](=O)[CH3:23])([O-:20])=[O:19].C([O-])(=O)C.[Na+].C([O-])(=O)C.[NH4+:34]>C(O)C>[CH3:23][C:22]1[N:34]=[C:11]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:5]([C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:4][C:21]=1[N+:18]([O-:20])=[O:19]

Participants

6

Reactant 4

HCID 40590Diethyl 2-(ethoxymethylidene)-3-oxobutanedioateHCID 662962-Propanone, 1-nitro-HCID 517045Sodium AcetateHCID 517165Ammonium Acetate

Product 1

HCID 18937855HCID 18937855, compoundYield 18.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
-10 °C

Procedure

Diethyl ethoxymethyleneoxalacetate (150.4 g, 0.616 mol, 1 eq) is dissolved in 300 mL absolute ethanol under a nitrogen atmosphere and the mixture is cooled to -10° C. in an ice/acetone bath. Unpurified 1-nitro-2-propanone (prepared by the method of D. Baker and S. Putt, Synthesis, 1978, 478-9, assumed to be 63.448 g, 0.616 mol) dissolved in 100 mL absolute ethanol is then added to the stirred solution. Sodium acetate (101.06 g, 1,232 mol) is then added in portions so that the temperature of the reaction remains below 10° C., followed by the addition of ammonium acetate (94.6 g, 1,232 g). The reaction mixture is allowed to warm to room temperature and is then stirred for 16 hours. The mixture is filtered through two pads of silica gel which are then eluted with methylene chloride. The filtrate is concentrated in vacuo to a thick dark oil which is chromatographed using hexanes as eluant, yielding the product in an 18.2% yield (31.4 g), having a melting point 90°-91.5° C.

Workup

  1. customPutt, Synthesis, 1978, 478-9
  2. additionis then added to the stirred solution
  3. customremains below 10° C.
  4. temperatureto warm to room temperature
  5. filtrationThe mixture is filtered through two pads of silica gel which
  6. washare then eluted with methylene chloride
  7. concentrationThe filtrate is concentrated in vacuo to a thick dark oil which
  8. customis chromatographed
  9. customyielding the product in an 18.2% yield (31.4 g)

Sources & evidence

ORD record
ord-4af9a95b3a8b4bef8857b77f0bf1229c
Source dataset
uspto-grants-1996_07
Patent number
US05534485

Reaction notes

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