Pyridine → 3-Chloro-N-hydroxy-2,2-dimethyl-N-phenylpropanamide

HRID 1995480Notes

Reaction equation

HRID 1995480 reaction equation
[Cl:1][CH2:2][C:3]([CH3:8])([CH3:7])[C:4](Cl)=[O:5].N1C=CC=CC=1.[C:15]1([NH:21][OH:22])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.CCCCCC>C(Cl)Cl>[Cl:1][CH2:2][C:3]([CH3:8])([CH3:7])[C:4]([N:21]([OH:22])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)=[O:5]

Participants

6

Reactant 4

HCID 1049PyridineHCID 7518N-PhenylhydroxylamineHCID 8058HexaneHCID 613453-Chloro-2,2-dimethylpropanoyl chloride

Product 1

HCID 131925163-Chloro-N-hydroxy-2,2-dimethyl-N-phenylpropanamideYield 25%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Under an argon atmosphere a stirred solution of 10.0 grams (0.065 mole) of 3-chloro-2,2-dimethylpropionyl chloride (prepared in the manner of Example 1, Step B) in 70 ml of methylene chloride was cooled to -70° and 6.1 grams (0.075 mole) of pyridine was added dropwise. A solution of 7.0 grams (0.065 mole) of N-phenylhydroxylamine in 30 ml of methylene chloride was then added dropwise over a 20-minute period. During the addition the reaction mixture temperature rose to -55°. Upon completion of addition the reaction mixture was stirred at -70° to -55° for 30 minutes, then was allowed to warm to ambient temperature where it was stirred for two hours. The reaction mixture was diluted with 100 ml of methylene chloride and washed with 100 ml of water, 100 ml of an aqueous 10% hydrochloric acid solution, and finally with 100 ml of water. The organic layer was dried by standing over magnesium sulfate for 16 hours. The darkened mixture was filtered and the filtrate concentrated under reduced pressure to give a black residue. The residue was slurried with 15 ml of hexane and the insolubles collected by filtration. The insoluble material was recrystallized from hexane/ethyl acetate to give 3.7 grams of 3-chloro-N-hydroxy-N-phenyl-2,2-dimethylpropanamide; mp 120°-121°.

Workup

  1. temperaturewas cooled to -70°
  2. additionDuring the addition the reaction mixture temperature
  3. customrose to -55°
  4. additionUpon completion of addition the reaction mixture
  5. stirringwas stirred for two hours
  6. washwashed with 100 ml of water, 100 ml of an aqueous 10% hydrochloric acid solution
  7. customThe organic layer was dried
  8. waitby standing over magnesium sulfate for 16 hours
  9. filtrationThe darkened mixture was filtered
  10. concentrationthe filtrate concentrated under reduced pressure
  11. customto give a black residue
  12. filtrationthe insolubles collected by filtration
  13. customThe insoluble material was recrystallized from hexane/ethyl acetate

Sources & evidence

ORD record
ord-66febb7663a04f828d1b770c10377951
Source dataset
uspto-grants-1983_09
Patent number
US04405357

Reaction notes

Loading…