Dicyclohexylcarbodiimide → HCID 178463104, compound

HRID 1275442Notes

Reaction equation

HRID 1275442 reaction equation
[C:1]([C:4]1[C:5]([CH3:20])=[C:6]2[C:11](=[C:12]([CH3:14])[CH:13]=1)[S:10](=[O:16])(=[O:15])[CH2:9][C:8]([CH3:18])([CH3:17])[C:7]2=[O:19])([OH:3])=O.[CH2:21]([N:23]1[C:27]([OH:28])=[CH:26][CH:25]=[N:24]1)[CH3:22].C1(N=C=NC2CCCCC2)CCCCC1.C(=O)([O-])[O-].[K+].[K+]>C(O)(CC)(C)C>[CH2:21]([N:23]1[C:27]([OH:28])=[C:26]([C:1]([C:4]2[C:5]([CH3:20])=[C:6]3[C:11](=[C:12]([CH3:14])[CH:13]=2)[S:10](=[O:15])(=[O:16])[CH2:9][C:8]([CH3:18])([CH3:17])[C:7]3=[O:19])=[O:3])[CH:25]=[N:24]1)[CH3:22]

Participants

6

Reactant 4

HCID 10868DicyclohexylcarbodiimideHCID 11430Potassium CarbonateHCID 15477826HCID 15477826, compoundHCID 178418331HCID 178418331, compound

Product 1

HCID 178463104HCID 178463104, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 64052-Methyl-2-butanolSolvent2×

Procedure

A 50-ml round-bottomed flask was charged with 0.51 g (1.72 mmol) of 6-carboxy-3,3,5,8-tetramethylthiochroman-4-one-1,1-dioxide, 0.21 g (1.88 mmol) of 1-ethyl-5-hydroxypyrazole and 5 ml of t-amyl alcohol, and while the mixture was stirred at room temperature, a solution of 0.42 g (2.04 mmol) of N,N'-dicyclohexylcarbodiimide in 2 ml of t-amyl alcohol was added. The mixture was further stirred at room temperature for 1 hour, and 0.18 g (1.30 mmol) of potassium carbonate was added to the reaction mixture. The mixture was heated at 80~90° C. for 8 hours. The solvent was distilled off under reduced pressure, and ethyl acetate and a 2 wt % sodium carbonate aqueous solution were added to the residue. An insoluble solid was removed by filtration. The mixture was separated into two phases, and an aqueous layer was neutralized and acidified with a 5 wt % hydrochloric acid aqueous solution, and a precipitated solid was extracted with ethyl acetate. An organic layer was washed with diluted hydrochloric acid and with a saturated sodium chloride aqueous solution, and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to give 0.55 g (yield 82%) of 6-(1-ethyl-5-hydroxypyrazol-4-yl)carbonyl-3,3,5,8-tetramethylthiochroman-4-one-1,1-dioxide in the form of a brown solid. This product was recrystallized from mixed solvents of ethyl acetate and n-hexane to give 0.36 g (yield 54%) of a white solid.

Workup

  1. stirringThe mixture was further stirred at room temperature for 1 hour
  2. temperatureThe mixture was heated at 80~90° C. for 8 hours
  3. distillationThe solvent was distilled off under reduced pressure, and ethyl acetate
  4. additiona 2 wt % sodium carbonate aqueous solution were added to the residue
  5. customAn insoluble solid was removed by filtration
  6. customThe mixture was separated into two phases
  7. extractiona precipitated solid was extracted with ethyl acetate
  8. washAn organic layer was washed with diluted hydrochloric acid and with a saturated sodium chloride aqueous solution
  9. dry with materialdried over anhydrous sodium sulfate
  10. distillationthe solvent was distilled off under reduced pressure

Sources & evidence

ORD record
ord-6f2e6b3df972463aaa1e298a6ed9e7c6
Source dataset
uspto-grants-2000_12
Patent number
US06159904

Reaction notes

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