Methanesulfonyl chloride → Sulfentrazone

HRID 1604018Notes

Reaction equation

HRID 1604018 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]>[Cl-].C[N+](C)(C)C.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

5

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 104.4%

Reagents, catalysts & solvents 2

HCID 6379Tetramethylammonium chlorideCatalystHCID 1140TolueneSolvent2×

Procedure

A 250-mL, three neck round bottomed flask was equipped with a mechanical stirrer, heating mantel, thermometer, pressure equalizing addition funnel and reflux condenser. A nitrogen purge was established across the top of the condenser with all gases exiting through a caustic scrubber. 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, 1.7 g (0.015 mole) of tetramethylammonium chloride (Aldrich, 97%) and 24 g 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 36 minutes. Ninety minutes after the completion of the addition, a further 3.9 mL (5.75 g, 0.05 mole) of methanesulfonyl chloride was added. After an additional 1.5 hours at reflux, the reaction mixture was diluted with 75 mL of toluene, transferred to a 1-L round bottomed flask equipped with a mechanical stirrer, and rinsed in with 100 mL of toluene. The mixture was allowed to cool to room temperature and stirred overnight (15.5 hours). The resulting slurry was cooled using an ice bath for three hours, the product collected by filtration, and the filter cake washed with a total of 155 ml of cold toluene and dried in a vacuum oven to provide 57.8 g (83% yield) of 80.3% assay 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. customA 250-mL, three neck round bottomed flask was equipped with a mechanical stirrer
  2. temperatureheating mantel
  3. additionaddition funnel
  4. temperaturereflux condenser
  5. customA nitrogen purge
  6. temperatureThe mixture was heated
  7. temperatureto reflux
  8. additionNinety minutes after the completion of the addition
  9. temperatureAfter an additional 1.5 hours at reflux
  10. customtransferred to a 1-L round bottomed flask
  11. customequipped with a mechanical stirrer
  12. washrinsed in with 100 mL of toluene
  13. temperatureThe resulting slurry was cooled
  14. customfor three hours
  15. filtrationthe product collected by filtration
  16. washthe filter cake washed with a total of 155 ml of cold toluene
  17. customdried in a vacuum oven

Sources & evidence

ORD record
ord-fe41e72f639743dfac0c7b9543ef352c
Source dataset
uspto-grants-1999_11
Patent number
US05990315

Reaction notes

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