Sulfuryl chloride → 4-Chloro-3-methyl-5-nitro-1H-pyrazole

HRID 2406057Notes

Reaction equation

HRID 2406057 reaction equation
[CH3:1][C:2]1[CH:6]=[C:5]([N+:7]([O-:9])=[O:8])[NH:4][N:3]=1.S(Cl)([Cl:13])(=O)=O>C(Cl)(Cl)Cl.CN(C=O)C>[Cl:13][C:6]1[C:2]([CH3:1])=[N:3][NH:4][C:5]=1[N+:7]([O-:9])=[O:8]

Participants

5

Reactant 2

HCID 24648Sulfuryl chlorideHCID 1354637365-Methyl-3-nitro-1H-pyrazole

Product 1

HCID 1355379634-Chloro-3-methyl-5-nitro-1H-pyrazoleYield 92%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6212ChloroformSolvent

Conditions

Temperature
115 °C

Procedure

Nitropyrazole 9 (10.0 g, 78.68 mmol) was dissolved in a mixture of chloroform (500 mL) with 1 drop DMF. To this was added sulfuryl chloride (9.60 mL, 14.33 g, 118.0 mmol) and the mixture heated to reflux for 20 hour at 115° C. external temperature. After additional 48 hours stirring at ambient temperature the mixture was evaporated to dryness in vacuo, dichloromethane (250 mL) added and the solution again evaporated in vacuo. Crude 15 was purified by column chromatography (1 kg SiO2, 0-10% methanol in DCM) yielding pure 15 (11.7 g, 72.42 mmol, 92%).

Workup

  1. temperaturethe mixture heated
  2. customwas evaporated to dryness in vacuo, dichloromethane (250 mL)
  3. additionadded
  4. customthe solution again evaporated in vacuo
  5. customCrude 15 was purified by column chromatography (1 kg SiO2, 0-10% methanol in DCM)

Sources & evidence

ORD record
ord-d87414d0afd745b78119f0c5823e0da0
Source dataset
uspto-grants-2014_08
Patent number
US08809344B2

Reaction notes

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