Benzaldehyde → HCID 19768819, compound

HRID 1590890Notes

Reaction equation

HRID 1590890 reaction equation
[Na].[CH:2](=[O:9])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Cl[CH:11](Cl)[C:12]([O:14][CH3:15])=[O:13].[NH2:17][C:18]([NH2:20])=O>CO.CCOCC.C(OCC)(=O)C>[NH2:20][C:18]1[O:9][C:2]([C:3]2[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=2)=[C:11]([C:12]([O:14][CH3:15])=[O:13])[N:17]=1

Participants

8

Reactant 4

HCID 240BenzaldehydeHCID 1176UreaHCID 8315Methyl dichloroacetateHCID 5360545Sodium

Product 1

HCID 19768819HCID 19768819, compoundYield 35%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3 g (0.13 gram atom) of sodium in 50 ml of methanol were added dropwise at 0°-5° within 20 minutes to a solution, cooled to 0°, of 16.1 g (152 mmol) of benzaldehyde and 20.0 g (140 mmol) of methyl dichloroacetate in 50 ml of ether. Thereafter, the reaction mixture was stirred at 0°-5° for a further 1.5 hours, then diluted with 100 ml of ethyl acetate and extracted with saturated sodium chloride solution. The organic phase was dried over magnesium sulfate and evaporated. The residue was dissolved in 50 mo of methanol and heated to reflux for 14 hours with 6.72 g (112 mmol) of urea. The reaction mixture was evaporated under reduced pressure, partitioned between methylene chloride and water, adjusted to pH 9 with conc. sodium hydroxide solution and extracted. The alkaline, aqueous phases were further extracted with methylene chloride. The organic phases were combined and washed twice with saturated sodium chloride solution, dried and evaporated. The residue was purified by medium pressure chromatography on 1 kg of silica gel. Elution with methylene chloride as well as methylene chloride/methanol 9:1 yield 8.4 g of an oil which crystallized from a mixture of methylene chloride, ether and hexane. In this manner there were obtained 4.7 g (35%) of methyl 2-amino-5-phenyl-4-oxazolecarboxylate as light yellowish crystals which were processed without further purification.

Workup

  1. extractionextracted with saturated sodium chloride solution
  2. dry with materialThe organic phase was dried over magnesium sulfate
  3. customevaporated
  4. dissolutionThe residue was dissolved in 50 mo of methanol
  5. temperatureheated
  6. customThe reaction mixture was evaporated under reduced pressure
  7. custompartitioned between methylene chloride and water
  8. extractionextracted
  9. extractionThe alkaline, aqueous phases were further extracted with methylene chloride
  10. washwashed twice with saturated sodium chloride solution
  11. customdried
  12. customevaporated
  13. customThe residue was purified by medium pressure chromatography on 1 kg of silica gel
  14. washElution with methylene chloride as well as methylene chloride/methanol 9:1 yield 8.4 g of an oil which
  15. customcrystallized from a mixture of methylene chloride, ether and hexane

Sources & evidence

ORD record
ord-5d8c5f5c0f7e412eb13e4dde53faf53b
Source dataset
uspto-grants-1993_04
Patent number
US05204482

Reaction notes

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