Benzene → HCID 54421021, compound

HRID 596214Notes

Reaction equation

HRID 596214 reaction equation
[OH:1][N:2]=[C:3]([C:9]([CH3:11])=[O:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5].[C:12](Cl)(Cl)=[O:13].ClC(ON=[C:21]([C:27]([CH3:29])=[O:28])C(OCC)=O)=O.[CH:30]1C=CC=CC=1>O.N1C=CC=CC=1.C(O)(C)(C)C>[C:27]([O:28][C:12]([O:1][N:2]=[C:3]([C:9]([CH3:11])=[O:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5])=[O:13])([CH3:29])([CH3:30])[CH3:21]

Participants

8

Reactant 4

HCID 241Benzene3×HCID 6371PhosgeneHCID 54491891Ethyl 2-{[(chlorocarbonyl)oxy]imino}-3-oxobutanoateHCID 178472877HCID 178472877, compound

Product 1

HCID 54421021HCID 54421021, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1049PyridineSolvent2×HCID 6386tert-ButanolSolvent

Procedure

A solution of ethyl 2-hydroxyiminoacetoacetate (3.98 g.) and pyridine (1.98 g.) in benzene (25 ml.) was dropwise added to a solution of phosgene (2.48 g.) in benzene (30 ml.) over 30 minutes at 4° to 5° C. After stirring for 1 hour at the same temperature, the mixture was stirred for 1 hour at room temperature and allowed to stand overnight. To the resultant solution containing ethyl 2-chlorocarbonyloxyiminoacetoacetate was dropwise added, over 30 minutes at 5° to 7° C, a solution of tert-butyl alcohol (3.7 g.) and pyridine (3.96 g.) in benzene (25 ml.). After stirring for 1 hour at the same temperature, the reaction temperature was slowly elevated to room temperature, after which the mixture was stirred for 6 hours at the same temperature and allowed to stand overnight. A precipitate was dissolved by adding about same volume of water to that of the organic layer to the reaction mixture, after which the aqueous layer was separated. The organic layer was in turn washed with a 0.5M citric acid aqueous solution, a 5% sodium carbonate aqueous solution and a sodium chloride aqueous solution, and dried over magnesium sulfate. After drying the solvent was distilled off to give ethyl 2-tert-butoxycarbonyloxyiminoacetoacetate (3.7 g.), oil.

Workup

  1. stirringthe mixture was stirred for 1 hour at room temperature
  2. waitto stand overnight
  3. additionwas dropwise added, over 30 minutes at 5° to 7° C
  4. stirringAfter stirring for 1 hour at the same temperature
  5. customwas slowly elevated to room temperature
  6. stirringafter which the mixture was stirred for 6 hours at the same temperature
  7. waitto stand overnight
  8. dissolutionA precipitate was dissolved
  9. customafter which the aqueous layer was separated
  10. washwashed with a 0.5M citric acid aqueous solution
  11. dry with materiala 5% sodium carbonate aqueous solution and a sodium chloride aqueous solution, and dried over magnesium sulfate
  12. customAfter drying the solvent
  13. distillationwas distilled off

Sources & evidence

ORD record
ord-483fe05f182947789b6e0e6aeff71e01
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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