Dimethylformamide → alpha-Chloro-2-nitrobenzenepropanoic acid 2,6-dimethylpiperidine salt

HRID 2231965Notes

Reaction equation

HRID 2231965 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].[CH3:31][CH:32]1[CH2:37][CH2:36][CH2:35][CH:34]([CH3:38])[NH:33]1>ClCCl.CCOCC>[CH3:31][CH:32]1[CH2:37][CH2:36][CH2:35][CH:34]([CH3:38])[NH:33]1.[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

8

Reactant 5

HCID 6228DimethylformamideHCID 24386Thionyl ChlorideHCID 68843NanofinHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 136517582-Hydroxy-3-(2-nitrophenyl)propanoic acid

Product 1

HCID 13651760alpha-Chloro-2-nitrobenzenepropanoic acid 2,6-dimethylpiperidine salt

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
25 °C

Procedure

To magnetically stirred N,N-dimethylformamide (2 ml, 25.8 mmol) cooled in ice was added slowly dropwise thionyl chloride (3 ml, 41.1 mmol), and the resulting cold Vilsmeier reagent was diluted with dichloromethane (10 ml). α-Hydroxy-2-nitrobenzenepropanoic acid (2.00 g, 9.47 mmol), followed by an additional 2 ml of dichloromethane was added. The mixture, protected from moisture, was stirred at room temperature (25° C.) overnight. The resulting solution was evaporated to a syrup. The syrup was dissolved in dichloromethane and the solution was added to stirred ice. The mixture was stirred for 1 hour during which time it warmed to room temperature. The dichloromethane solution was separated and washed (X4) with water and dried (MgSO4). Evaporation gave a syrup which was subjected to an oil pump vacuum for half an hour. The syrup was dissolved in ether and 2,6-dimethylpiperidine was added to approximate neutrality (pH 9 with pH paper). The crude titled product [2.36 g (81%), mp 138°-140° C.] crystallized readily. Recrystallization (methanol-ether) with decolorization (Nuchar C-190N) gave pure product, mp 141°-143° C.

Workup

  1. additionwas added
  2. customThe resulting solution was evaporated to a syrup
  3. dissolutionThe syrup was dissolved in dichloromethane
  4. additionthe solution was added
  5. stirringto stirred ice
  6. stirringThe mixture was stirred for 1 hour during which time it
  7. temperaturewarmed to room temperature
  8. customThe dichloromethane solution was separated
  9. washwashed (X4) with water
  10. dry with materialdried (MgSO4)
  11. customEvaporation
  12. customgave a syrup which
  13. waitwas subjected to an oil pump vacuum for half an hour
  14. customThe crude titled product [2.36 g (81%), mp 138°-140° C.] crystallized readily
  15. customRecrystallization (methanol-ether) with decolorization (Nuchar C-190N)
  16. customgave pure product, mp 141°-143° C.

Sources & evidence

ORD record
ord-86d8298c8c0b42d18792f0af1f7754c9
Source dataset
uspto-grants-1988_11
Patent number
US04785118

Reaction notes

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