Pyridine → HCID 12165618, compound

HRID 2252019Notes

Reaction equation

HRID 2252019 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:10]=[CH:11][C:12]=1[N+:13]([O-:15])=[O:14])[C:7]([OH:9])=O)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.Cl.[CH3:23][NH:24][O:25][CH3:26].N1C=CC=CC=1>CN(C)C=O.ClCCl>[CH3:23][N:24]([O:25][CH3:26])[C:7](=[O:9])[C:6]1[CH:10]=[CH:11][C:12]([N+:13]([O-:15])=[O:14])=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1

Participants

7

Reactant 4

HCID 1049PyridineHCID 107093,4-Dinitrobenzoic acidHCID 65578Oxalyl chlorideHCID 81138Methanamine, N-methoxy-, hydrochloride (1:1)

Product 1

HCID 12165618HCID 12165618, compoundYield 77.5%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

Cool a mixture of 3,4-dinitrobenzoic acid (195 g, 0.92 moles), 1.3 L of dry dichloromethane, and 2 mL dimethylformamide to −12° C. under a nitrogen atmosphere. Add oxalyl chloride (134 ml, 1.54 moles) dropwise via addition funnel over 35 minutes and stir the reaction mixture at room temperature under a nitrogen atmosphere overnight. Remove excess oxalyl chloride from the reaction mixture by repetitive cycles of concentrating a dichloromethane solution of the reaction mixture under reduced pressure. Cool a mixture of the residue in 1 L dichloromethane to −5° C. under a nitrogen atmosphere and add N,O-dimethylhydroxylamine hydrochloride (98.7 g, 1.01 moles) followed by the careful addition of 209 mL (2.62 moles) of dry pyridine in portions. Stir the mixture at room temperature for 4 hours and then concentrate under reduced pressure. Suspend the residue in 500 mL dichloromethane and concentrate under reduced pressure twice. Suspend the residue in 500 mL dichloromethane and filter. Store the filtrate at −13° C. for 3 days, filter the solid and rinse with cold dichloromethane. Dilute the filtrate with water (40 mL) and stored at −13° C. again to provide a second crop. Dry the combined crops under reduced pressure to provide 182 g (77%) of the desired compound.

Workup

  1. temperatureCool
  2. concentrationRemove excess oxalyl chloride from the reaction mixture by repetitive cycles of concentrating a dichloromethane solution of the reaction mixture under reduced pressure
  3. temperatureCool
  4. additiona mixture of the residue in 1 L dichloromethane to −5° C. under a nitrogen atmosphere
  5. stirringStir the mixture at room temperature for 4 hours
  6. concentrationconcentrate under reduced pressure
  7. concentrationconcentrate under reduced pressure twice
  8. filtrationfilter
  9. waitStore the filtrate at −13° C. for 3 days
  10. filtrationfilter the solid
  11. washrinse with cold dichloromethane
  12. additionDilute the filtrate with water (40 mL)
  13. customstored at −13° C.
  14. customto provide a second crop
  15. customDry the combined crops under reduced pressure

Sources & evidence

ORD record
ord-a28d57bcfbcb4f8092a271a3aeae178c
Source dataset
uspto-grants-2008_01
Patent number
US07320995B2

Reaction notes

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