Dimethylformamide → alpha-Chloro-2-Nitrobenzenepropanoic Acid

HRID 2231966Notes

Reaction equation

HRID 2231966 reaction equation
CN(C)C=O.S(Cl)(Cl)=O.C[N+](C)=C[Cl:13].[Cl-].O[CH:17]([CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[N+:28]([O-:30])=[O:29])[C:18]([OH:20])=[O:19]>ClCCl>[Cl:13][CH:17]([CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[N+:28]([O-:30])=[O:29])[C:18]([OH:20])=[O:19]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 136517582-Hydroxy-3-(2-nitrophenyl)propanoic acid

Product 1

HCID 13220464alpha-Chloro-2-Nitrobenzenepropanoic AcidYield 90%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a magnetically stirred N,N-dimethylformamide (20 ml, 258.5 mmol) cooled in ice was added slowly dropwise thionyl chloride (30 ml, 411.2 mmol). To the resulting cold Vilsmeier reagent was added dichloromethane (100 ml), α-hydroxy-2-nitrobenzenepropanoic acid (20.0 g, 94.7 mmol) and a further 50 mL of dichloromethane as a rinse. The mixture, protected from extraneous moisture, was stirred at room temperature until solution was achieved and the solution was left at room temperature (25° C.) overnight. The solution was poured onto stirred ice and the mixture stirred for 1 hour during which time it warmed to room temperature. The dichloromethane layer was separated, washed thrice with water, dried (MgSO4) and evaporated to a syrup. The syrup was concentrated further at 40° C. under oil pump vacuum to remove traces of N,N-dimethylformamide. The resulting syrup was stirred magnetically with water while while cooling in ice. The resulting solid was ground in a mortar and collected on a filter. The solid was then stirred magnetically with water, collected on a filter and washed with water. Drying under vacuum over phosphorus pentoxide at room temperature provided 19.60 g (90%) of titled product, mp 107°-109° C.

Workup

  1. additionThe solution was poured
  2. stirringonto stirred ice
  3. stirringthe mixture stirred for 1 hour during which time it
  4. temperaturewarmed to room temperature
  5. customThe dichloromethane layer was separated
  6. washwashed thrice with water
  7. dry with materialdried (MgSO4)
  8. customevaporated to a syrup
  9. concentrationThe syrup was concentrated further at 40° C. under oil pump vacuum
  10. customto remove traces of N,N-dimethylformamide
  11. stirringThe resulting syrup was stirred magnetically with water while
  12. temperaturewhile cooling in ice
  13. customcollected on a filter
  14. stirringThe solid was then stirred magnetically with water
  15. customcollected on
  16. filtrationa filter
  17. washwashed with water
  18. dry with materialDrying under vacuum over phosphorus pentoxide at room temperature

Sources & evidence

ORD record
ord-a0a6af2333bd4a20ac050855eaa959bd
Source dataset
uspto-grants-1988_11
Patent number
US04785118

Reaction notes

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