Pyridine → HCID 532191, compound

HRID 1484539Notes

Reaction equation

HRID 1484539 reaction equation
[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=O.C(Cl)(=O)C(Cl)=O.N1C=CC=CC=1.[N+:23]([C:26]1[CH:27]=[C:28]([CH:30]=[CH:31][CH:32]=1)[NH2:29])([O-:25])=[O:24]>C(OCC)(=O)C.Cl.CN(C)C=O.ClCCl>[Br:1][C:2]1[CH:10]=[CH:9][CH:8]=[CH:7][C:3]=1[C:4]([NH:29][C:28]1[CH:30]=[CH:31][CH:32]=[C:26]([N+:23]([O-:25])=[O:24])[CH:27]=1)=[O:6]

Participants

9

Conditions

Temperature
45 °C

Procedure

2-Bromobenzoic acid (5.02 g, 25.0 mmol) was sealed in a 250 mL flask with stir bar under nitrogen. Dichloromethane (72 mL) was then added and the solution was cooled on ice. Oxalyl chloride (2.19 ml, 25.0 mmol) and N,N-dimethylformamide (17 μL, 0.22 mmol) were added, and the reaction was removed from the ice bath and the resulting suspension was stirred for 20 h with a vent to an oil bubbler. After this time, the pale yellow solution was cooled on ice, then pyridine (4.04 ml, 50.0 mmol) and 3-nitroaniline (3.00 g, 21.7 mmol) were added. The reaction was then removed from the ice bath, and a water condenser was attached to the flask. The reaction was heated in an oil bath at 45° C., and after 1 h LC-MS analysis showed the reaction to be complete. The reaction was diluted with ethyl acetate (250 mL) and 1 M aqueous HCl (100 mL), then the layers were separated and the organic phase was washed again with aqueous HCl, then twice with half-saturated aqueous NaHCO3, then brine. The organics were dried over Na2SO4, filtered, and concentrated to a yellow solid, which was dried and pulverized several times, yielding the title compound (6.89 g, 99%). LRMS (ESI+) (M+H): 321.01.

Workup

  1. temperaturethe solution was cooled on ice
  2. customthe reaction was removed from the ice bath
  3. stirringthe resulting suspension was stirred for 20 h with a vent to an oil bubbler
  4. temperatureAfter this time, the pale yellow solution was cooled on ice
  5. customThe reaction was then removed from the ice bath, and a water condenser
  6. customthe reaction
  7. customthe layers were separated
  8. washthe organic phase was washed again with aqueous HCl
  9. dry with materialThe organics were dried over Na2SO4
  10. filtrationfiltered
  11. concentrationconcentrated to a yellow solid, which
  12. customwas dried

Sources & evidence

ORD record
ord-c6d36f40ecd94bf4bc65feffff758f83
Source dataset
uspto-grants-2016_08
Patent number
US09422262B2

Reaction notes

Loading…