Water → HCID 54571280, compound

HRID 1614499Notes

Reaction equation

HRID 1614499 reaction equation
[C:1]1([CH2:7][S:8]([NH2:11])(=[O:10])=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].[C:14]([C:16]1[CH:17]=[N:18][N:19]([C:26]2[C:31]([Cl:32])=[CH:30][C:29]([C:33]([F:36])([F:35])[F:34])=[CH:28][N:27]=2)[C:20]=1[CH:21]=[CH:22][C:23](Cl)=[O:24])#[N:15].O>O1CCCC1>[C:1]1([CH2:7][S:8]([NH:11][C:23](=[O:24])[CH:22]=[CH:21][C:20]2[N:19]([C:26]3[C:31]([Cl:32])=[CH:30][C:29]([C:33]([F:36])([F:35])[F:34])=[CH:28][N:27]=3)[N:18]=[CH:17][C:16]=2[C:14]#[N:15])(=[O:9])=[O:10])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 78318BenzenemethanesulfonamideHCID 53679607HCID 53679607, compound

Product 1

HCID 54571280HCID 54571280, compoundYield 26.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of 0.31 gram (0.002 mole) of phenylmethanesulfonamide in 15 mL of tetrahydrofuran was added 0.05 gram (0.002 mole) of sodium hydride which was washed into the reaction vessel with 10 mL of tetrahydrofuran. The reaction mixture was warmed to reflux temperature, and a solution of 0.32 gram (0.001 mole) of 3-[4-cyano-1-(3-chloro-5-trifluoromethylpyridin-2-yl)-1H-pyrazol-5-yl]acrylic acid chloride in 5 mL of tetrahydrofuran was added dropwise during a 20 minute period. Upon completion of the addition, heating of the reaction mixture at reflux was continued for 75 minutes. After this time, the reaction mixture was cooled, and 1 mL of water was added. The mixture was concentrated under reduced pressure to a residue. The residue was dissolved in 35 mL of water, and the solution was acidified with aqueous 4N hydrochloric acid. The resultant solid was collected by filtration, and the filter cake was washed with water. The filter cake was then stirred with hot water. The hot water was decanted away from a semi-solid material. The semi-solid was stirred with fresh cold water which caused the semi-solid to totally solidify. The solid was collected by filtration and was then dissolved in 1:1 toluene/ethyl acetate. The solution was passed through a column of silica gel. The eluate was concentrated under reduced pressure, yielding 0.13 gram of N-phenylmethanesulfonyl-3-[4-cyano-1-(3-chloro-5-trifluoromethylpyridin-2-yl)-1H-pyrazol-5-yl]acrylamide. The nmr spectrum was consistent with the proposed structure.

Workup

  1. washwas washed into the reaction vessel with 10 mL of tetrahydrofuran
  2. temperatureThe reaction mixture was warmed
  3. temperatureto reflux temperature
  4. additionUpon completion of the addition
  5. temperatureheating of the reaction mixture
  6. temperatureat reflux
  7. temperatureAfter this time, the reaction mixture was cooled
  8. concentrationThe mixture was concentrated under reduced pressure to a residue
  9. dissolutionThe residue was dissolved in 35 mL of water
  10. filtrationThe resultant solid was collected by filtration
  11. washthe filter cake was washed with water
  12. customThe hot water was decanted away from a semi-solid material
  13. stirringThe semi-solid was stirred with fresh cold water which
  14. filtrationThe solid was collected by filtration
  15. dissolutionwas then dissolved in 1:1 toluene/ethyl acetate
  16. concentrationThe eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-f45f81cf7210484ba6cac78ad3942075
Source dataset
uspto-grants-1993_03
Patent number
US05198014

Reaction notes

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