Dicyclohexylcarbodiimide → HCID 178463112, compound

HRID 1252643Notes

Reaction equation

HRID 1252643 reaction equation
[CH2:1]([N:3]1[C:7]([OH:8])=[CH:6][CH:5]=[N:4]1)[CH3:2].[Cl:9][C:10]1[CH:18]=[C:17]([S:19]([CH3:22])(=[O:21])=[O:20])[CH:16]=[CH:15][C:11]=1[C:12](O)=[O:13].C1(N=C=NC2CCCCC2)CCCCC1.C(=O)([O-])[O-].[K+].[K+]>>[CH2:1]([N:3]1[C:7]([OH:8])=[C:6]([C:12](=[O:13])[C:11]2[CH:15]=[CH:16][C:17]([S:19]([CH3:22])(=[O:21])=[O:20])=[CH:18][C:10]=2[Cl:9])[CH:5]=[N:4]1)[CH3:2]

Participants

5

Reactant 4

HCID 10868DicyclohexylcarbodiimideHCID 11430Potassium CarbonateHCID 7358632-Chloro-4-(methylsulfonyl)benzoic acidHCID 178418331HCID 178418331, compound

Product 1

HCID 178463112HCID 178463112, compoundYield 82%

Conditions

Temperature
90 °C

Procedure

After 2.35 g (0.021 mol) of 1-ethyl-5-hydroxypyrazole was dissolved in 20 ml of tert.-amyl alcohole, the mixture was succesively added with 4.69 g (0.02 mol) of 2-chloro-4-methanesulfonyl benzoic acid, 5.33 g (0.021 mol) of N,N'-dicyclohexyl carbodiimide and 1.52 g (0.011 mol) of anhydrous potassium carbonate, and heated at 50°-60° C. for 5 hours, followed by additional stirring for 1 hour at 90° C. Then, the reaction was ceased. After cooling, solvent was distilled off from the reaction solution, and the residue was added with 50 ml of 5% aqueous solution of potassium hydroxide to dissolve the soluble matter. After insoluble matter was filtered off, the aqueous layer was washed with chloroform and separated. This operation was twice carried out. The obtained aqueous layer was adjusted to pH <1 by adding concentrated hydrochloric acid, and the precipitated solid product was dissolved in chloroform and extracted. After the chloroform layer was dried over sodium sulfate anhydrate, the solvent was distilled off to give a crude product of the objective product. Then, the crude product was recrystallized from 95% ethanol to obtain 5.38 g of 1-ethyl-4-(2-chloro-4-methanesulfonylbenzoyl)-5-hydroxypyrazole.

Workup

  1. temperatureheated at 50°-60° C. for 5 hours
  2. temperatureAfter cooling
  3. distillationsolvent was distilled off from the reaction solution
  4. additionthe residue was added with 50 ml of 5% aqueous solution of potassium hydroxide
  5. dissolutionto dissolve the soluble matter
  6. filtrationAfter insoluble matter was filtered off
  7. washthe aqueous layer was washed with chloroform
  8. customseparated
  9. additionby adding concentrated hydrochloric acid
  10. dissolutionthe precipitated solid product was dissolved in chloroform
  11. extractionextracted
  12. dry with materialAfter the chloroform layer was dried over sodium sulfate anhydrate
  13. distillationthe solvent was distilled off
  14. customto give a crude product of the objective product
  15. customThen, the crude product was recrystallized from 95% ethanol

Sources & evidence

ORD record
ord-c431ce9a4404471590f9f1b31131849b
Source dataset
uspto-grants-1988_05
Patent number
US04744815

Reaction notes

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