Dimethylformamide → 4'-Cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilide

HRID 1356666Notes

Reaction equation

HRID 1356666 reaction equation
[Na].[C:2]([C:4]1[CH:20]=[CH:19][C:7]([NH:8][S:9]([C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[CH:14][CH:13]=2)(=[O:11])=[O:10])=[C:6]([N+:21]([O-:23])=[O:22])[CH:5]=1)#[N:3].CN(C=O)C.[CH:29](I)([CH3:31])[CH3:30]>O>[C:2]([C:4]1[CH:20]=[CH:19][C:7]([N:8]([CH:29]([CH3:31])[CH3:30])[S:9]([C:12]2[CH:13]=[CH:14][C:15]([CH3:18])=[CH:16][CH:17]=2)(=[O:11])=[O:10])=[C:6]([N+:21]([O-:23])=[O:22])[CH:5]=1)#[N:3]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 6362Isopropyl iodideHCID 698226864'-Cyano-2'-nitro-p-toluenesulfonanilide sodium salt

Product 1

HCID 185092034'-Cyano-N-isopropyl-2'-nitro-p-toluenesulfonanilideYield 8.8%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

To a mixture of 4′-cyano-2′-nitro-p-toluenesulfonanilide sodium salt (1330 g (3.92 mol)) and DMF (3000 ml), under heating in an oil bath kept at 110° C., isopropyl iodide (2019 g (11.8 mol)) was added over a period of 1.5 hours. After completion of the addition, the mixture was further heated at the same temperature with stirring for 3 hours, and then left to cool to room temperature. Water (1500 ml) was added to bring about separation of crystals. The crystals were filtered, washed with water, dried, and then suspended in diethyl ether. The suspension was stirred for 4 hours, and the insolubles were removed by filtration, the diethyl ether solution was washed with 0.1% aqueous sodium hydroxide solution to remove the remaining starting material, 4′-cyano-2′-nitro-p-toluenesulfonanilide. The diethyl ether layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to give crude crystals which were, after washing with ethanol, recrystallized from ethyl acetate to give 124 g (8.8%) of the title compound as pale yellow crystals.

Workup

  1. temperatureunder heating in an oil bath
  2. customkept at 110° C.
  3. additionAfter completion of the addition
  4. temperaturethe mixture was further heated at the same temperature
  5. waitleft
  6. customto bring about separation of crystals
  7. filtrationThe crystals were filtered
  8. washwashed with water
  9. customdried
  10. stirringThe suspension was stirred for 4 hours
  11. customthe insolubles were removed by filtration
  12. washthe diethyl ether solution was washed with 0.1% aqueous sodium hydroxide solution
  13. customto remove the
  14. dry with materialThe diethyl ether layer was dried over anhydrous magnesium sulfate
  15. filtrationfiltered
  16. concentrationconcentrated under reduced pressure
  17. customto give crude crystals which
  18. washafter washing with ethanol
  19. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-962d7c22699c412ba26e6318207be4a1
Source dataset
uspto-grants-2003_07
Patent number
US06586617B1

Reaction notes

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