Thionyl Chloride → 1-(2,6-Dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfenyl-5-(pyrazin-2-ylmethylamino)pyrazole-3-carbonitrile

HRID 22867Notes

Reaction equation

HRID 22867 reaction equation
[F:1][C:2]([F:7])([F:6])[S:3]([O-])=O.[K+].C1(C)C=CC(S(O)(=O)=O)=CC=1.CNC.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.S(Cl)(Cl)=O.[Cl:39][C:40]1[CH:45]=[C:44]([C:46]([F:49])([F:48])[F:47])[CH:43]=[C:42]([Cl:50])[C:41]=1[N:51]1[C:55]([NH:56][CH2:57][C:58]2[CH:63]=[N:62][CH:61]=[CH:60][N:59]=2)=[CH:54][C:53]([C:64]#[N:65])=[N:52]1.C(=O)([O-])O.[Na+]>ClCCCl>[Cl:50][C:42]1[CH:43]=[C:44]([C:46]([F:47])([F:48])[F:49])[CH:45]=[C:40]([Cl:39])[C:41]=1[N:51]1[C:55]([NH:56][CH2:57][C:58]2[CH:63]=[N:62][CH:61]=[CH:60][N:59]=2)=[C:54]([S:3][C:2]([F:7])([F:6])[F:1])[C:53]([C:64]#[N:65])=[N:52]1

Participants

8

Reactant 6

HCID 24386Thionyl ChlorideHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 2733643Potassium trifluoromethanesulphinateHCID 112007821-(2,6-Dichloro-4-trifluoromethylphenyl)-5-(pyrazin-2-ylmethylamino)pyrazole-3-carbonitrileHCID 12199009Dimethylamine p-toluenesulfonate

Product 1

HCID 111798181-(2,6-Dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfenyl-5-(pyrazin-2-ylmethylamino)pyrazole-3-carbonitrileYield 38%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

Into 5.0 ml of 1,2-dichloroethane were suspended 1.725 g (10.0 mmol) of potassium trifluoromethanesulfinate, 895 mg (4.1 mmol) of dimethylamine p-toluenesulfonate, 951 mg (5.0 mmol) of p-toluenesulfonic acid monohydrate, and then 1.506 g (12.6 mmol) of thionyl chloride was added under ice-cooling. After 3 hours of stirring at room temperature, 1.03 g (2.5 mmol) of 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(pyrazin-2-ylmethylamino)pyrazole-3-carbonitrile was added thereto, and the mixture was warmed to 40° C. and stirred for 5 hours. The reaction mixture was neutralized with saturated aqueous sodium hydrogen carbonate solution and then extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure and the resulting oil was purified to isolate 487 mg (yield 38%) of 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfenyl-5-(pyrazin-2-ylmethylamino)pyrazole-3-carbonitrile.

Workup

  1. temperaturecooling
  2. temperaturethe mixture was warmed to 40° C.
  3. stirringstirred for 5 hours
  4. extractionextracted with dichloromethane
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. customThe solvent was removed by distillation under reduced pressure
  7. customthe resulting oil was purified

Sources & evidence

ORD record
ord-9f5dacb5fb6147e4a36b33c4f4d15450
Source dataset
uspto-grants-2005_02
Patent number
US06849633B2

Reaction notes

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