Methanesulfonic Acid → HCID 178516451, compound

HRID 1758555Notes

Reaction equation

HRID 1758555 reaction equation
[Cl:1][C:2]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][C:3]=1[NH:4][C:5](=[N:19]O)[CH2:6][C:7]([NH:9][C:10]1[C:15]([Cl:16])=[CH:14][C:13]([Cl:17])=[CH:12][C:11]=1[Cl:18])=[O:8].C(OC(=O)C)(=O)C.CS(O)(=O)=O.C(N(C1CC(=O)N(C2C(Cl)=CC(Cl)=CC=2Cl)N=1)C1C=C([N+]([O-])=O)C=CC=1Cl)(=O)C.C(N(C1C=C(OC(=O)C)N(C2C(Cl)=CC(Cl)=CC=2Cl)N=1)C1C=C([N+]([O-])=O)C=CC=1Cl)(=O)C>O.C(O)(=O)C>[Cl:1][C:2]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][C:3]=1[NH:4][C:5]1[CH2:6][C:7](=[O:8])[N:9]([C:10]2[C:15]([Cl:16])=[CH:14][C:13]([Cl:17])=[CH:12][C:11]=2[Cl:18])[N:19]=1

Participants

8

Reactant 5

HCID 6395Methanesulfonic AcidHCID 7918Acetic AnhydrideHCID 13802995HCID 13802995, compoundHCID 13802997HCID 13802997, compoundHCID 178520852HCID 178520852, compound

Product 1

HCID 178516451HCID 178516451, compoundYield 42%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Procedure

In a 5 L three-necked flask, equipped with a stirrer, a reflux condenser, and a thermometer, were placed 226 g of 3-(2-chloro-5-nitroanilino)-3-oximino-N-(2,4,6-trichlorophenyl)propionamide, 2 L of glacial acetic acid, and 500 mL of acetic anhydride. The mixture was stirred at room temperature for 18 hours. The yellow color of the slurry turned almost colorless, and thin layer chromatography (TLC) showed that the O-acetyloximino derivative was the sole product. To the reaction mixture was added 50 g of methanesulfonic acid and the mixture was heated as quickly as possible to its boiling point, 117°-120° C., and kept under reflux for 10 minutes. TLC showed that the reaction was essentially complete at that time and gave a mixture of 3-(N-acetyl-2-chloro-5-nitroanilino)-1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-one and 3-(N-acetyl-2-chloro-5-nitroanilino)-5-acetyloxy-1-(2,4,6-trichlorophenyl)pyrazole. At the end of the heating period, the reflux condenser was quickly replaced with a distillation head, and a water-aspirator vacuum was carefully applied to distill off the solvent as well as to cool down the mixture to 50°-60° C. The distillation of solvent was continued keeping the pot temperature at 50°-60° C. until no more distillate came off. The resulting dark greenish brown viscous oil was dissolved in 2 L of methanol with heat, and 500 mL of concentrated hydrochloric acid in water was added slowly through a dropping funnel. The mixture was heated under reflux for 1 hour, cooled to room temperature, and then allowed to stand at room temperature overnight. The solid was collected, washed with methanol and water, and dried. There was obtained 91 g (42%) of the desired 3-(2-chloro-5-nitroanilino)-1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-one, having a melting point of 278°-280° C.

Workup

  1. customIn a 5 L three-necked flask, equipped with a stirrer, a reflux condenser
  2. temperaturethe mixture was heated as quickly as possible to its boiling point, 117°-120° C.
  3. temperatureunder reflux for 10 minutes
  4. customgave
  5. distillationto distill off the solvent as well as
  6. temperatureto cool down the mixture to 50°-60° C
  7. distillationThe distillation of solvent
  8. customat 50°-60° C.
  9. dissolutionThe resulting dark greenish brown viscous oil was dissolved in 2 L of methanol
  10. temperaturewith heat
  11. addition500 mL of concentrated hydrochloric acid in water was added slowly through a dropping funnel
  12. temperatureThe mixture was heated
  13. temperatureunder reflux for 1 hour
  14. temperaturecooled to room temperature
  15. waitto stand at room temperature overnight
  16. customThe solid was collected
  17. washwashed with methanol and water
  18. customdried

Sources & evidence

ORD record
ord-6eb33c80f4d249ed8b7a6cca7db1b09a
Source dataset
uspto-grants-1983_02
Patent number
US04374253

Reaction notes

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