Benzene → HCID 54421021, compound

HRID 597679Notes

Reaction equation

HRID 597679 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 added dropwise to a solution of phosgene (2.48 g.) in benzene (30 ml.) for 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. A solution of tert-butyl alcohol (3.7 g.) and pyridine (3.96 g.) in benzene (25 ml.) was added dropwise for 30 minutes at 5° to 7° C. to the resultant solution containing ethyl 2-chlorocarbonyloxyiminoacetoacetate. 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 as dissolved by adding about the same volume of water as that of the organic layer to the reaction mixture. The aqueous layer was then separated. The organic layer was then 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. stirringAfter stirring for 1 hour at the same temperature
  4. customwas slowly elevated to room temperature
  5. stirringafter which the mixture was stirred for 6 hours at the same temperature
  6. waitto stand overnight
  7. dissolutionA precipitate as dissolved
  8. customThe aqueous layer was then separated
  9. washThe organic layer was then washed with a 0.5M citric acid aqueous solution
  10. dry with materiala 5% sodium carbonate aqueous solution and a sodium chloride aqueous solution, and dried over magnesium sulfate
  11. customAfter drying
  12. distillationthe solvent was distilled off

Sources & evidence

ORD record
ord-8ccc9c2f6a8448c186620bbe7f7ae938
Source dataset
uspto-grants-1977_03
Patent number
US04014915

Reaction notes

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