Phenylbutazone → 1,2-Diphenyl-4-butyl-5(4'-methylphenylsulfonyloxy)-4-pyrazolin-3-one

HRID 259179Notes

Reaction equation

HRID 259179 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][C:4]([S:7](Cl)(=[O:9])=[O:8])=[CH:3][CH:2]=1.CN(C)C=O.[Tl+].[CH3:18][CH2:19][CH2:20][CH2:21][CH:22]1[C:27](=[O:28])[N:26]([C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[N:25]([C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[C:23]1=[O:24]>CCOCC>[C:35]1([N:25]2[C:23]([O:24][S:7]([C:4]3[CH:5]=[CH:6][C:1]([CH3:11])=[CH:2][CH:3]=3)(=[O:9])=[O:8])=[C:22]([CH2:21][CH2:20][CH2:19][CH3:18])[C:27](=[O:28])[N:26]2[C:29]2[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=2)[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1

Participants

6

Reactant 4

HCID 4781Phenylbutazone2×HCID 6228DimethylformamideHCID 73974-Toluenesulfonyl chlorideHCID 105005Thallous cation2×

Product 1

HCID 122520271,2-Diphenyl-4-butyl-5(4'-methylphenylsulfonyloxy)-4-pyrazolin-3-oneYield 33%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Then, p-Toluenesulfonyl chloride (0.95 g, 5.0 mmole) was allowed to react with a dimethylformamide (20 ml) suspension of the Thallium (I) salt of phenylbutazone. Within a few minutes the solvent became pink and a yellow solid, instead of the white Thallium (I) salt of phenylbutazone, was observed suspended in the pink solution. The suspension was stirred overnight in a tightly sealed flask, then it was diluted with 100 ml of ether and filtered. The filtrate was concentrated in vacuo to remove the ether and the dimethylformamide was evaporated under a stream of nitrogen. The residue from the evaporation was suspended in dichloromethane and filtered. Analysis of the filtrate by TLC showed that it contained only one major component. The dichloromethane was evaporated in vacuo and the residue was crystallized from ether to give 0.76 g (mp 112°-121° C., 33% yield) of yellow crystals which contained only one components by TLC analysis. Recrystallization of the yellow crystals gave analytically pure crystals, mp 125°-127° C. with spectral properties identical to the crystals, mp 112°-121° C.

Workup

  1. waitWithin a few minutes the solvent became pink
  2. filtrationfiltered
  3. concentrationThe filtrate was concentrated in vacuo
  4. customto remove the ether
  5. customthe dimethylformamide was evaporated under a stream of nitrogen
  6. customThe residue from the evaporation
  7. filtrationfiltered
  8. customThe dichloromethane was evaporated in vacuo
  9. customthe residue was crystallized from ether

Sources & evidence

ORD record
ord-547eb28d89414d0a9fcff64dba6f8067
Source dataset
uspto-grants-1977_07
Patent number
US04036845

Reaction notes

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