Methyl acetoacetate → HCID 12720322, compound

HRID 258111Notes

Reaction equation

HRID 258111 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].C[O-].[Na+].Cl[C:13](=[N:18]O)[C:14]([O:16][CH3:17])=[O:15]>CO>[CH3:5][C:3]1[O:4][N:18]=[C:13]([C:14]([O:16][CH3:17])=[O:15])[C:2]=1[C:1]([O:7][CH3:8])=[O:6]

Participants

5

Reactant 3

HCID 7757Methyl acetoacetateHCID 10942334Sodium MethoxideHCID 85058881HCID 85058881, compound

Product 1

HCID 12720322HCID 12720322, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent3×

Procedure

23.2 g (0.2 mol) of methyl acetoacetate in 50 ml of absolute methanol are added to a solution of 10.8 g (0.2 mol) of sodium methylate (cryst.) in 150 ml of dry methanol at 0°-10° C., and the mixture is stirred at this temperature for 3 h. Subsequently, at 0°-10° C., 27.5 g (0.2 mol) of methyl α-chloro-α-hydroximinoacetate in 100 ml of absolute methanol are slowly added dropwise, and the mixture is stirred at room temperature for 12 h. The solution is worked up by evaporation to a small volume and addition of 800 ml of water, when the product separates out as oil. The organic phase is separated off, the aqueous phase is extracted with dichloromethane, the combined organic phases are dried, and the solvent is stripped off in a rotary evaporator. The residue is purified by column chromatography on silica gel (solvent cyclohexane/ethyl acetate 3:1). 15.1 g (38% of theory) of dimethyl 5-methylisoxazole- 3,4-dicarboxylate are obtained.

Workup

  1. stirringthe mixture is stirred at room temperature for 12 h
  2. customThe solution is worked up by evaporation to a small volume and addition of 800 ml of water, when the product
  3. customThe organic phase is separated off
  4. extractionthe aqueous phase is extracted with dichloromethane
  5. customthe combined organic phases are dried
  6. customthe solvent is stripped off in a rotary evaporator
  7. customThe residue is purified by column chromatography on silica gel (solvent cyclohexane/ethyl acetate 3:1)

Sources & evidence

ORD record
ord-db505868fb654b74953ac1bd9d1e0230
Source dataset
uspto-grants-1993_11
Patent number
US05264580

Reaction notes

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