2-dimethylsulfamoyl-5-phenoxymethyl-2H-pyrazole-3-carboxylic acid methoxy-methyl-amide → 5-Acetyl-3-phenoxymethyl-pyrazole-1-sulfonic acid dimethylamide

HRID 1773785Notes

Reaction equation

HRID 1773785 reaction equation
[CH3:1][Mg]Br.CON(C)[C:7]([C:9]1[N:10]([S:22](=[O:27])(=[O:26])[N:23]([CH3:25])[CH3:24])[N:11]=[C:12]([CH2:14][O:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:13]=1)=[O:8]>C1(C)C=CC=CC=1.C1COCC1.[NH4+].[Cl-]>[CH3:25][N:23]([CH3:24])[S:22]([N:10]1[C:9]([C:7](=[O:8])[CH3:1])=[CH:13][C:12]([CH2:14][O:15][C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)=[N:11]1)(=[O:26])=[O:27]

Participants

6

Reactant 2

HCID 866738982-dimethylsulfamoyl-5-phenoxymethyl-2H-pyrazole-3-carboxylic acid methoxy-methyl-amideHCID 178418573HCID 178418573, compound2×

Product 1

HCID 679600925-Acetyl-3-phenoxymethyl-pyrazole-1-sulfonic acid dimethylamideYield 89%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 8028TetrahydrofuranSolvent3×HCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
-78 °C

Procedure

A 1.4M solution of methylmagnesium bromide in toluene and THF (3.88 mL, 5.43 mmol) was added to a solution of 2-dimethylsulfamoyl-5-phenoxymethyl-2H-pyrazole-3-carboxylic acid methoxy-methyl-amide (1.54 g, 4.17 mmol) in THF (20 mL) at −78° C. and under nitrogen. The mixture was stirred at −78° C. for 1 hour and then at room temperature for 16 hours. Then, a second portion of methylmagnesium bromide in toluene and THF (3.58 mL, 5.01 mmol) was added at 0° C. and the mixture was stirred at room temperature for 3 hours. The mixture was diluted with a saturated solution of NH4Cl and extracted with AcOEt. The organic layer was separated, dried (Na2SO4), filtered and the solvents evaporated in vacuo. The crude product was purified by flash column chromatography (silica; AcOEt in heptane 0/100 to 50/50). The desired fractions were collected and the solvents evaporated in vacuo to yield 5-acetyl-3-phenoxymethyl-pyrazole-1-sulfonic acid dimethylamide (1.2 g, 89% yield) as a white solid.

Workup

  1. waitat room temperature for 16 hours
  2. stirringthe mixture was stirred at room temperature for 3 hours
  3. extractionextracted with AcOEt
  4. customThe organic layer was separated
  5. dry with materialdried (Na2SO4)
  6. filtrationfiltered
  7. customthe solvents evaporated in vacuo
  8. customThe crude product was purified by flash column chromatography (silica; AcOEt in heptane 0/100 to 50/50)
  9. customThe desired fractions were collected
  10. customthe solvents evaporated in vacuo

Sources & evidence

ORD record
ord-6bddd701d1654d92b67816c707fd38fd
Source dataset
uspto-grants-2016_02
Patent number
US09255103B2

Reaction notes

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