Dimethylformamide → HCID 53954290, compound

HRID 1182306Notes

Reaction equation

HRID 1182306 reaction equation
P(Cl)(Cl)(Cl)=O.[F:6][C:7]([F:19])([F:18])[C:8]1[CH:13]=[CH:12][C:11]([CH2:14][C:15]([OH:17])=O)=[CH:10][CH:9]=1.C(=O)([O-])[O-].[K+].[K+].[OH-].[Na+].[CH3:28][N:29]([CH3:32])[CH:30]=O>>[CH3:28][N:29]([CH3:32])[CH:30]=[C:14]([C:11]1[CH:10]=[CH:9][C:8]([C:7]([F:6])([F:19])[F:18])=[CH:13][CH:12]=1)[CH:15]=[O:17]

Participants

6

Reactant 5

HCID 6228Dimethylformamide2×HCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 118342(alpha,alpha,alpha-Trifluoro-4-tolyl)acetic acid

Product 1

HCID 53954290HCID 53954290, compound

Procedure

To 13.70 mL (146.95 mmol) of phosphorus oxychloride at 0° C. was added 13.92 mL (179.77 mmol) of anhydrous N,N-dimethylformamide dropwise. The resulting solution was stirred for 15 min at room temperature. Then, 10.00 g (48.98 mmol) of [4-(trifluoromethyl)phenyl]acetic acid in 24 mL of anhydrous N,N-dimethylformamide was added dropwise. The resulting mixture was stirred for 19 h at 70° C., and then poured onto ice. Following neutralization with potassium carbonate, 30 g of sodium hydroxide was added, and the resulting solution was heated at 50° C. for 15 min. It was then cooled to 0° C. and filtered. The filter cake was washed with water and dried under a vacuum to give 3-(dimethylamino)-2-[4-(trifluoromethyl)phenyl]-2-propenal. This dry solid was dissolved in 122 mL of methanol, 3.07 mL (97.97 mmol) of hydrazine was added, and the solution was stirred for 6 h at room temperature. It was poured into water, and the resulting mixture was filtered. The filter cake was washed with water, followed by hexanes, and dried under vacuum to give 8.35 g (80% yield) of 4-[4-(trifluoro)phenyl]-1H-pyrazole. Rf=0.26 (1:19 methanol:dichloromethane); 1H-NMR (300 MHz, DMSO-d6): δ 13.09 (br s, 1H), 8.34 (s, 1H), 8.04 (s, 1H), 7.82 (d, J=8 Hz, 2H), 7.68 (d, J=8 Hz, 2H); ES-LCMS m/z 213 (M+H).

Workup

  1. stirringThe resulting mixture was stirred for 19 h at 70° C.
  2. additionpoured onto ice
  3. additionwas added
  4. temperaturethe resulting solution was heated at 50° C. for 15 min
  5. temperatureIt was then cooled to 0° C.
  6. filtrationfiltered
  7. washThe filter cake was washed with water
  8. customdried under a vacuum

Sources & evidence

ORD record
ord-42c88fefcc3b4f1aa82464e609c97052
Source dataset
uspto-grants-2007_10
Patent number
US07288541B2

Reaction notes

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