Pyridine → HCID 86746073, compound

HRID 846816Notes

Reaction equation

HRID 846816 reaction equation
C[N:2](C)C=O.C(Cl)(=O)C(Cl)=O.[CH2:12]([O:19][C:20]1[CH:28]=[CH:27][C:23]([C:24]([OH:26])=O)=[C:22]([NH:29][C:30]([CH3:32])=[O:31])[CH:21]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.N1C=CC=CC=1.[N+:39]([C:42]1[CH:48]=[CH:47][CH:46]=[CH:45][C:43]=1N)([O-:41])=[O:40]>C(OCC)(=O)C.[OH-].[Na+]>[N+:39]([C:42]1[CH:48]=[CH:47][CH:46]=[CH:45][C:43]=1[C:21]1[C:22]([NH:29][C:30]([CH3:32])=[O:31])=[C:23]([CH:27]=[CH:28][C:20]=1[O:19][CH2:12][C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:24]([NH2:2])=[O:26])([O-:41])=[O:40]

Participants

8

Reactant 5

HCID 1049Pyridine2×HCID 6228DimethylformamideHCID 69462-NitroanilineHCID 65578Oxalyl chlorideHCID 18452829HCID 18452829, compound

Product 1

HCID 86746073HCID 86746073, compound

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolvent3×HCID 14798Sodium HydroxideSolvent

Procedure

28.5 g (0.39 mole) dry dimethylformamide in 910 mL dry ethyl acetate are mixed dropwise at 2° C., under an atmosphere of nitrogen, with 21.5 g (0.17 mole) oxalyl chloride. After stirring for 30 minutes at 2°-5° C., a suspension of 37.2 g (0.13 mole) 4-benzyloxyacetaminobenzoic acid and 14.4 g (0.18 mole) pyridine in 65 mL ethyl acetate are added thereto and the ice bath is removed. After stirring for 2.5 hours at ambient temperature, the reaction mixture is mixed with a solution of 19.8 g (0.14 mole) o-nitroaniline and 14.4 g (0.18 mole) pyridine in 65 mL ethyl acetate. After stirring for 1 hour at ambient temperature, the reaction mixture is heated to the boil for 3 hours. After cooling, it is mixed with 500 mL IN aqueous sodium hydroxide solution and the phases are separated. The aqueous phase is shaken out twice with ethyl acetate. The combined organic phases are washed neutral with water and dried over anhydrous sodium sulfate. The solvent is evaporated to 150 mL and the precipitated crystals are filtered off with suction and recrystallized from 700 mL ethanol. Yield 13 g (24.7% of theory); m.p 128°-130° C.

Workup

  1. additionare added
  2. customthe ice bath is removed
  3. stirringAfter stirring for 2.5 hours at ambient temperature
  4. stirringAfter stirring for 1 hour at ambient temperature
  5. temperaturethe reaction mixture is heated to the boil for 3 hours
  6. temperatureAfter cooling
  7. customthe phases are separated
  8. stirringThe aqueous phase is shaken out twice with ethyl acetate
  9. washThe combined organic phases are washed neutral with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. customThe solvent is evaporated to 150 mL
  12. filtrationthe precipitated crystals are filtered off with suction
  13. customrecrystallized from 700 mL ethanol
  14. customm.p 128°-130° C.

Sources & evidence

ORD record
ord-71883f19644140dc95ddb5f67aa4f417
Source dataset
uspto-grants-1992_08
Patent number
US05137918

Reaction notes

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