4-Fluorophenylhydrazine hydrochloride → 5-[3,5-difluoro-4-(methylthio)-phenyl]-1-(4-fluorophenyl)-3-(trifluoromethyl)-1H-pyrazole

HRID 1838497Notes

Reaction equation

HRID 1838497 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([C:11](=O)[CH2:12][C:13](=O)[C:14]([F:17])([F:16])[F:15])[CH:5]=[C:6]([F:10])[C:7]=1[S:8][CH3:9].Cl.[F:21][C:22]1[CH:27]=[CH:26][C:25]([NH:28][NH2:29])=[CH:24][CH:23]=1>C(O)C.Cl>[F:1][C:2]1[CH:3]=[C:4]([C:11]2[N:28]([C:25]3[CH:26]=[CH:27][C:22]([F:21])=[CH:23][CH:24]=3)[N:29]=[C:13]([C:14]([F:17])([F:16])[F:15])[CH:12]=2)[CH:5]=[C:6]([F:10])[C:7]=1[S:8][CH3:9]

Participants

5

Reactant 2

HCID 699814-Fluorophenylhydrazine hydrochlorideHCID 227465181-[3,5-Difluoro-4-(methylthio)phenyl]-4,4,4-trifluorobutane-1,3-dione

Product 1

HCID 227457735-[3,5-difluoro-4-(methylthio)-phenyl]-1-(4-fluorophenyl)-3-(trifluoromethyl)-1H-pyrazole

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidCatalystHCID 702EthanolSolvent

Procedure

1-[3,5-difluoro-4-(methylthio)phenyl]-4,4,4-trifluoro-butane-1,3-dione (1.09 g, 3.6 mmol) dissolved in ethanol (150 mL). One drop of concentrated hydrochloric acid was added and 4-fluorophenylhydrazine hydrochloride (0.69 g, 4.0 mmol). The reaction was stirred at ambient temperature for 72 hours. Solvent was removed in vacuo and the residue was dissolved in ethyl acetate (100 mL) extracted with water (2×100 mL), saturated ammonium chloride (2×150 mL) and dried over sodium sulfate. The solvent was removed in vacuo and the 5-[3,5-difluoro-4-(methylthio)-phenyl]-1-(4-fluorophenyl)-3-(trifluoromethyl)-1H-pyrazole was obtained by crystallization from ethyl acetate and hexanes (0.71 g, 50%). 1H NMR (CDCl3/300 MHz) 7.36-7.29 (m, 2H), 7.18-7.13 (m, 2H), 6.81-6.77 (m, 3H), 2.53 (s, 3H). ESHRMS m/z 389.0557 (M+H+, Calcd 389.0547). Anal. Calcd for C17H10F6N2S: C, 52.58; H, 2.34; N, 7.21; Found: C, 52.45; H, 2.34; N, 7.15.

Workup

  1. customSolvent was removed in vacuo
  2. dissolutionthe residue was dissolved in ethyl acetate (100 mL)
  3. extractionextracted with water (2×100 mL), saturated ammonium chloride (2×150 mL)
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was removed in vacuo

Sources & evidence

ORD record
ord-e4736fe2c88e4864a35b7ee69cd036c0
Source dataset
uspto-grants-2004_01
Patent number
US06673818B2

Reaction notes

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