Methanesulfonyl chloride → Sulfentrazone

HRID 1604019Notes

Reaction equation

HRID 1604019 reaction equation
[NH2:1][C:2]1[C:3]([Cl:19])=[CH:4][C:5]([Cl:18])=[C:6]([N:8]2[C:12](=[O:13])[N:11]([CH:14]([F:16])[F:15])[C:10]([CH3:17])=[N:9]2)[CH:7]=1.[CH3:20][S:21](Cl)(=[O:23])=[O:22]>C1(C)C=CC=CC=1>[Cl:19][C:3]1[CH:4]=[C:5]([Cl:18])[C:6]([N:8]2[C:12](=[O:13])[N:11]([CH:14]([F:15])[F:16])[C:10]([CH3:17])=[N:9]2)=[CH:7][C:2]=1[NH:1][S:21]([CH3:20])(=[O:23])=[O:22]

Participants

4

Reactant 2

HCID 31297Methanesulfonyl chloride2×HCID 110559662-(5-Amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one

Product 1

HCID 86369SulfentrazoneYield 79%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

The reaction was carried out using the same equipment as described in Example 1. The flask was charged with 53.9 g (0.143 mole, 82% assay) of 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one and 24 grams of toluene. The mixture was heated to reflux and 15.6 mL (23 g, 0.20 mole) of methanesulfonyl chloride (Aldrich, 99.5%) added dropwise over 22 minutes. The solution was heated at reflux for 4.5 hours after the completion of the addition, and a further 3.9 mL (5.75 g, 0.05 mole) of methanesulfonyl chloride was added over 10 minutes. After an additional 2.5 hours at reflux, the reaction mixture was diluted with 75 mL of toluene, allowed to cool to room temperature, and stirred over the weekend (62 hours). The resulting slurry was warmed to dissolve the solids, transferred to a 1-L round bottomed flask equipped with a mechanical stirrer, and rinsed in with 200 mL of toluene. The mixture was warmed to 80° C. and washed twice with 150 mL portions of water, with the washes being removed via pipette. The solution was allowed to cool slowly to 40° C. and the resulting slurry then cooled in an ice bath for 2.5 hours. The product was collected by filtration and the filter cake washed with a total of 120 mL of cold toluene and dried in a vacuum oven to provide 48.6 g (79% yield) of 90% assay of N-[2,4-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]phenyl]methanesulfonamide as a tan solid.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux
  3. temperatureThe solution was heated
  4. temperatureat reflux for 4.5 hours
  5. additionafter the completion of the addition
  6. temperatureAfter an additional 2.5 hours at reflux
  7. temperatureThe resulting slurry was warmed
  8. dissolutionto dissolve the solids
  9. customtransferred to a 1-L round bottomed flask
  10. customequipped with a mechanical stirrer
  11. washrinsed in with 200 mL of toluene
  12. temperatureThe mixture was warmed to 80° C.
  13. washwashed twice with 150 mL portions of water, with the washes
  14. custombeing removed via pipette
  15. temperatureto cool slowly to 40° C.
  16. temperaturethe resulting slurry then cooled in an ice bath for 2.5 hours
  17. filtrationThe product was collected by filtration
  18. washthe filter cake washed with a total of 120 mL of cold toluene
  19. customdried in a vacuum oven

Sources & evidence

ORD record
ord-5af632d4e114499191eac6b5e968fe13
Source dataset
uspto-grants-1999_11
Patent number
US05990315

Reaction notes

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