Acetic Acid → Dimethyl 2-(carbamoylamino)benzene-1,4-dicarboxylate

HRID 1672445Notes

Reaction equation

HRID 1672445 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[NH2:14].CC(O)=O.[O-:20][C:21]#[N:22].[K+].[O-]C#N>O>[NH2:22][C:21]([NH:14][C:5]1[CH:6]=[C:7]([C:8]([O:10][CH3:11])=[O:9])[CH:12]=[CH:13][C:4]=1[C:3]([O:2][CH3:1])=[O:15])=[O:20]

Participants

6

Reactant 4

HCID 176Acetic Acid2×HCID 79336Dimethyl aminoterephthalateHCID 11378442Potassium cyanateHCID 178513472HCID 178513472, compound

Product 1

HCID 40151776Dimethyl 2-(carbamoylamino)benzene-1,4-dicarboxylate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To a 1 L flask charged with 2-aminoterephthalic acid dimethyl ester (29.4 g, 141 mmol) was added AcOH (160 mL) and the suspension heated to 60° C. until a solution was formed. A solution of potassium cyanate (23.4 g, 288 mmol) in water (50 mL) was then added to the stirred solution at 60° C. Effervescence was seen and a white ppt crashed out immediately, hindering stirring. AcOH was added (70 mL) to aid stirring and the suspension was stirred at 75° C. for 7 hrs. Another 1 eq of cyanate added portion wise (dry). More effervescence was seen and the reaction left for 16 hours at 70° C. The reaction was cooled to 0° C. and the product ppt was filtered off, the flask washed with water to get all product out. The material was washed with water (150 mL) and air dried o/n under vacuum. The crude product was suspended in MeOH (300 mL) and stirred under reflux for 1 hour. The suspension was cooled to room temperature and filtered. The product was washed with cold MeOH (300 mL) and ether and dried in vacuo to afford the title compound as a white solid, 31.5 g, 89%. 1H NMR (400 MHz, DMSO-D6) δ ppm 9.71 (1H, s) 8.97 (1H, s) 7.98 (1H, d, J=8.08 Hz) 7.46-7.57 (1H, m) 6.73 (2H, s) 3.88 (6H, s).

Workup

  1. customwas formed
  2. stirringto aid stirring
  3. stirringthe suspension was stirred at 75° C. for 7 hrs
  4. temperatureThe reaction was cooled to 0° C.
  5. filtrationthe product ppt was filtered off
  6. washthe flask washed with water
  7. customto get all product out
  8. washThe material was washed with water (150 mL) and air
  9. customdried o/n under vacuum
  10. stirringstirred
  11. temperatureunder reflux for 1 hour
  12. temperatureThe suspension was cooled to room temperature
  13. filtrationfiltered
  14. washThe product was washed with cold MeOH (300 mL) and ether
  15. customdried in vacuo

Sources & evidence

ORD record
ord-8952713ae93e4222a35212627620af23
Source dataset
uspto-grants-2011_08
Patent number
US07998978B2

Reaction notes

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