Hydrochloric Acid → 3-Ureidobenzoic acid

HRID 1451067Notes

Reaction equation

HRID 1451067 reaction equation
[NH2:1][C:2]([NH2:4])=[O:3].N[C:6]1[CH:7]=[C:8]([CH:12]=[CH:13][CH:14]=1)[C:9]([OH:11])=[O:10].Cl>CN(C)C=O.O>[C:9]([C:8]1[CH:7]=[C:6]([NH:1][C:2]([NH2:4])=[O:3])[CH:14]=[CH:13][CH:12]=1)([OH:11])=[O:10]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 1176UreaHCID 74193-Aminobenzoic Acid

Product 1

HCID 2959793-Ureidobenzoic acidYield 20%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 962WaterSolvent2×

Procedure

Urea (17.5 g, 0.292 mol), m-aminobenzoic acid (Aldrich, 10.0 g, 0.073 mol), water (30 mL), and concentrated HCl (3 mL) were added to a 125-mL Erlenmeyer flask and boiled for 45 min. The brown suspension became a purple solution on boiling and a brown precipitate formed after 15 min. The pH of the solution was 7 after 45 min. The mixture was cooled on ice and a mauve solid was collected by filtration, slurried with water, and again collected by filtration. The solid was added to 50 mL boiling ethanol and dimethylformamide (DMF, 25 mL) was added by drop until the solid dissolved. No precipitate formed on cooling. Water was added with stirring until turbidity and then a few drops of DMF were added to give a clear solution. The solution was cooled on ice and a light-purple solid was collected by filtration. Water was added to the filtrate to precipitate a tan solid which was also collected by filtration. The tan solid was dissolved in 5% sodium bicarbonate and neutralized with a 10% solution of potassium bisulfate. The tan solid was collected by filtration, washed with water, and dried in vacuo. The tan solid was then recrystallized from 700 mL methanol and 300 mL water. After cooling, a purple solid was collected by filtration. The product was precipitated from the filtrate with the addition of 1 L of water. This light-tan solid was collected on a filter and dried in vacuo. The product was dissolved in 175 mL boiling ethanol and the volume was reduced to 75 mL and filtered while hot. This was slowly cooled to room temperature and then on ice to give an off-white solid. This solid was collected on a filter, washed with cold ethanol, and dried in vacuo to give 2.5 g (20%) of the title compound, mp 276°-280° C.

Workup

  1. customa brown precipitate formed after 15 min
  2. customafter 45 min
  3. temperatureThe mixture was cooled on ice
  4. filtrationa mauve solid was collected by filtration
  5. filtrationagain collected by filtration
  6. additionThe solid was added to 50 mL
  7. additionwas added by drop until the solid
  8. dissolutiondissolved
  9. customNo precipitate formed
  10. temperatureon cooling
  11. customto give a clear solution
  12. temperatureThe solution was cooled on ice
  13. filtrationa light-purple solid was collected by filtration
  14. additionWater was added to the filtrate
  15. customto precipitate a tan solid which
  16. filtrationwas also collected by filtration
  17. dissolutionThe tan solid was dissolved in 5% sodium bicarbonate
  18. filtrationThe tan solid was collected by filtration
  19. washwashed with water
  20. customdried in vacuo
  21. customThe tan solid was then recrystallized from 700 mL methanol and 300 mL water
  22. temperatureAfter cooling
  23. filtrationa purple solid was collected by filtration
  24. customThe product was precipitated from the filtrate with the addition of 1 L of water
  25. customThis light-tan solid was collected on
  26. filtrationa filter
  27. customdried in vacuo
  28. dissolutionThe product was dissolved in 175 mL
  29. filtrationfiltered while hot
  30. customon ice to give an off-white solid
  31. customThis solid was collected on a filter
  32. washwashed with cold ethanol
  33. customdried in vacuo

Sources & evidence

ORD record
ord-7b8fa8cf6469449a8567d7723c55c6cb
Source dataset
uspto-grants-1997_02
Patent number
US05602277

Reaction notes

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