Nitric Acid → 1-(2-Fluoro-4-chloro-5-methylsulfonyloxyphenyl)-3,5-dimethyl-4-nitropyrazole

HRID 580268Notes

Reaction equation

HRID 580268 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([O:9][S:10]([CH3:13])(=[O:12])=[O:11])=[CH:4][C:3]=1[N:14]1[C:18]([CH3:19])=[CH:17][C:16]([CH3:20])=[N:15]1.S(=O)(=O)(O)O.[N+:26]([O-])([OH:28])=[O:27]>O>[F:1][C:2]1[CH:7]=[C:6]([Cl:8])[C:5]([O:9][S:10]([CH3:13])(=[O:12])=[O:11])=[CH:4][C:3]=1[N:14]1[C:18]([CH3:19])=[C:17]([N+:26]([O-:28])=[O:27])[C:16]([CH3:20])=[N:15]1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 1118Sulfuric Acid2×HCID 137982511-(2-Fluoro-4-chloro-5-methylsulfonyloxyphenyl)-3,5-dimethylpyrazole

Product 1

HCID 142557491-(2-Fluoro-4-chloro-5-methylsulfonyloxyphenyl)-3,5-dimethyl-4-nitropyrazoleYield 90.9%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To 1-(2-fluoro-4-chloro-5-methylsulfonyloxyphenyl)-3,5-dimethylpyrazole (31.9 g) was added 95% sulfuric acid (35 ml) and then added dropwise an acid mixture of 95% sulfuric acid (7.5 ml) and 61% nitric acid (10.3 g) under cooling with iced water, and the reaction mixture was stirred at room temperature for further one hour, and was then poured into iced water. The reaction mixture was extracted with toluene and the resulting toluene layer was washed with 1N aqueous sodium hydroxide solution and then with water and dried over anhydrous sodium sulfate. Removal of the solvent from.the extract in toluene by distillation in vacuo gave the titled compound (33.1 g) as a yellowish brown crystalline solid. Recrystallization of the solid from a mixture of cyclohexane/acetone yielded a pale yellow crystalline solid. m.p. 150.5°-152.5° C.

Workup

  1. additionadded dropwise
  2. extractionThe reaction mixture was extracted with toluene
  3. washthe resulting toluene layer was washed with 1N aqueous sodium hydroxide solution
  4. dry with materialwith water and dried over anhydrous sodium sulfate
  5. customRemoval of the solvent
  6. extractionfrom.the extract in toluene by distillation in vacuo

Sources & evidence

ORD record
ord-2d1ecbbb4e1f459e8f83156527947ed3
Source dataset
uspto-grants-1988_06
Patent number
US04752326

Reaction notes

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