1-(4-Chlorophenyl)-4,4,4-trifluorobutane-1,3-dione → 4-(5-(4-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamide

HRID 1356884Notes

Reaction equation

HRID 1356884 reaction equation
[F:1][C:2]([F:16])([F:15])[C:3](=O)[CH2:4][C:5]([C:7]1[CH:12]=[CH:11][C:10]([Cl:13])=[CH:9][CH:8]=1)=O.ClC1C=CC(C2C(C(F)(F)F)=[N:26][N:27]([C:29]3[CH:34]=[CH:33][C:32]([S:35]([NH2:38])(=[O:37])=[O:36])=[CH:31][CH:30]=3)C=2)=CC=1.ClC1C=CC(C2C=C(C(F)(F)F)N(C3C=CC(S(N)(=O)=O)=CC=3)N=2)=CC=1>C(O)C>[Cl:13][C:10]1[CH:11]=[CH:12][C:7]([C:5]2[N:27]([C:29]3[CH:30]=[CH:31][C:32]([S:35]([NH2:38])(=[O:37])=[O:36])=[CH:33][CH:34]=3)[N:26]=[C:3]([C:2]([F:16])([F:15])[F:1])[CH:4]=2)=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 27738321-(4-Chlorophenyl)-4,4,4-trifluorobutane-1,3-dioneHCID 10111682HCID 10111682, compoundHCID 10763602HCID 10763602, compound

Product 1

HCID 98658084-(5-(4-Chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl)benzenesulfonamideYield 80%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

4-Sulphonamidophenylhydrazine hydrochloride (982 mg, 4.4 mmol 1,1-equivalent) was added to a stirred solution of 4,4,4-trifluoro-1-[4-(chloro)phenyl]-butane-1,3-dione from Step 1 (1.00 g, 4.0 mmol) in ethanol 150 mL). The reaction was heated to reflux and stirred for 20 hours. (HPLC area percent showed a 96:3 ratio of 4-[4-(4-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenesulfonamide to its regioisomer (4-[3-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrazol-1-yl]benzenesulfonamide. After cooling to room temperature, the reaction mixture was concentrated in vacuo. The residue was taken up in ethyl acetate, washed with water and with brine, dried over MgSO4, filtered, and concentrated in vacuo to give a light brown solid which was recrystallized from ethyl acetate and iso-octane to give the pyrazole (1.28 g, 80%, mp 143-145° C.). HPLC showed that the purified material was a 99.5:0.5 mixture of 4-[5-(4-chlorophenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenesulfonamide to its regioisomer. 1H NMR (CDCl3/CD3OD 10/1) d 5.2 (s, 2H), 6.8 (s, 1H), 7.16 (d, j=8.5 Hz, 2H), 7.35 (d, j=8.5 Hz, 2H), 7.44 (d, j=8.66, 2H), 7.91 (d, j=8.66, 2H.); 13C NMR (CDCl3/CD3OD 10/1) d 106.42 (d, j=0.03 Hz), 121.0 (q, j=276 Hz), 125.5, 126.9, 127.3, 129.2, 130.1, 135.7, 141.5, 143.0, 143.9 (q, j=37 Hz), 144.0; 19F NMR (CDCl3/CD3OD 10/1) d −62.9. EI GC-MS M+=401.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux
  3. concentrationthe reaction mixture was concentrated in vacuo
  4. washwashed with water and with brine
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give a light brown solid which
  9. customwas recrystallized from ethyl acetate and iso-octane

Sources & evidence

ORD record
ord-38f1fabfa7144d30b243f09318b9d6c6
Source dataset
uspto-grants-2003_07
Patent number
US06586603B1

Reaction notes

Loading…