Acetic Anhydride → HCID 66939432, compound

HRID 1257303Notes

Reaction equation

HRID 1257303 reaction equation
[F:1][C:2]([F:12])([F:11])[C:3](=O)[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH:13]([O-])([O-])OCC.C(OC(=O)C)(=O)C.[NH2:26][NH:27][C:28]([NH2:30])=[S:29].[Cl:31][CH2:32][C:33](=O)[CH2:34]Cl>C(OCC)(=O)C.O.C(O)C>[Cl:31][CH2:32][C:33]1[N:30]=[C:28]([N:27]2[C:3]([C:2]([F:12])([F:11])[F:1])=[C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH:13]=[N:26]2)[S:29][CH:34]=1

Participants

9

Reactant 5

HCID 7918Acetic AnhydrideHCID 107931,3-DichloroacetoneHCID 67793Ethyl 4,4,4-trifluoroacetoacetateHCID 2723789ThiosemicarbazideHCID 53630039Ethylorthoformate

Product 1

HCID 66939432HCID 66939432, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of ethyl 4,4,4-trifluoroacetoacetate (28.56 g), ethyl orthoformate (40 mL) and acetic anhydride (45 ml) was heated under reflux for 4 hr, and cooled to room temperature. Ethanol (240 ml) and thiosemicarbazide (10.95 g) were added, and the mixture was stirred at room temperature for 2 hr. 1,3-Dichloropropanone (15.20 g) was added, and the mixture was further heated under reflux for 16 hr, cooled to room temperature, and diluted with ethyl acetate and water. The ethyl acetate layer was separated, washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate) to give a crude title compound (11.4 g) as crystals

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 4 hr
  3. temperaturethe mixture was further heated
  4. temperatureunder reflux for 16 hr
  5. temperaturecooled to room temperature
  6. customThe ethyl acetate layer was separated
  7. washwashed with saturated aqueous sodium hydrogen carbonate
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography (carrier: silica gel, eluent: hexane-ethyl acetate)

Sources & evidence

ORD record
ord-50c74ffae75f4611a23de9e9d002b680
Source dataset
uspto-grants-2013_06
Patent number
US08461348B2

Reaction notes

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