tert-Butyl carbazate → HCID 58244228, compound

HRID 389094Notes

Reaction equation

HRID 389094 reaction equation
C(OC(C)(C)C)(=O)[NH:2][NH2:3].[Cl:10][C:11]1[CH:23]=[CH:22][C:14]([O:15][C:16]([CH3:21])([CH3:20])[C:17](O)=[O:18])=[C:13]([F:24])[CH:12]=1>CN(C)C1C=CN=CC=1.C(#N)C>[Cl:10][C:11]1[CH:23]=[CH:22][C:14]([O:15][C:16]([CH3:21])([CH3:20])[C:17]([NH:2][NH2:3])=[O:18])=[C:13]([F:24])[CH:12]=1

Participants

5

Reactant 2

HCID 70091tert-Butyl carbazateHCID 57467471HCID 57467471, compound

Product 1

HCID 58244228HCID 58244228, compoundYield 68.6%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

WSC•monohydrochloride (18.1 g), tert-butyl carbazate (10.5 g) and 4-(dimethylamino)pyridine (461 mg) were sequentially added to a solution of 2-(4-chloro-2-fluorophenoxy)-2-methylpropanoic acid (17.6 g) in acetonitrile (170 ml), followed by stirring at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure and ethyl acetate was then added thereto. The organic layer was washed with water, 0.5M hydrochloric acid, saturated aqueous sodium bicarbonate solution-water (1:1) and then saturated brine in this order and was dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure. The resulting oil (21.8 g) was dissolved in ethyl acetate, 4M hydrogen chloride-ethyl acetate was added thereto, followed by stirring at room temperature for 5 hours and was then concentrated under reduced pressure. Ethyl acetate was added thereto, followed by stirring and the solid was thus separated by filtration. Saturated aqueous sodium bicarbonate was added to the solid thus obtained, followed by extraction with ethyl acetate. The organic layer was washed with saturated brine-water (1:1) and then saturated brine in this order and was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain, as a colorless oil, 2-(4-chloro-2-fluorophenoxy)-2-methylpropanohydrazide (12.8 g).

Workup

  1. concentrationThe reaction solution was concentrated under reduced pressure and ethyl acetate
  2. additionwas then added
  3. washThe organic layer was washed with water, 0.5M hydrochloric acid, saturated aqueous sodium bicarbonate solution-water (1:1)
  4. dry with materialsaturated brine in this order and was dried over anhydrous sodium sulfate
  5. customthe solvent was evaporated under reduced pressure
  6. dissolutionThe resulting oil (21.8 g) was dissolved in ethyl acetate
  7. addition4M hydrogen chloride-ethyl acetate was added
  8. stirringby stirring at room temperature for 5 hours
  9. concentrationwas then concentrated under reduced pressure
  10. additionEthyl acetate was added
  11. stirringby stirring
  12. customthe solid was thus separated by filtration
  13. additionSaturated aqueous sodium bicarbonate was added to the solid
  14. customthus obtained
  15. extractionfollowed by extraction with ethyl acetate
  16. washThe organic layer was washed with saturated brine-water (1:1)
  17. dry with materialsaturated brine in this order and was dried over anhydrous sodium sulfate
  18. customthe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-f564b47362ba4458be046d7e263a6a27
Source dataset
uspto-grants-2013_02
Patent number
US08377923B2

Reaction notes

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