Tert-Butyl nitrite → 1-(4-Fluorophenyl)-5-[4-(methylthio)phenyl]-pyrazole

HRID 654788Notes

Reaction equation

HRID 654788 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N:8]2[C:12]([C:13]3[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=3)=[CH:11][C:10](N)=[N:9]2)=[CH:4][CH:3]=1.N(OC(C)(C)C)=O>C(#N)C.O1CCOCC1>[F:1][C:2]1[CH:3]=[CH:4][C:5]([N:8]2[C:12]([C:13]3[CH:18]=[CH:17][C:16]([S:19][CH3:20])=[CH:15][CH:14]=3)=[CH:11][CH:10]=[N:9]2)=[CH:6][CH:7]=1

Participants

5

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 107565811-(4-Fluorophenyl)-5-[4-(methylthio)phenyl]-3-pyrazolamine

Product 1

HCID 107317821-(4-Fluorophenyl)-5-[4-(methylthio)phenyl]-pyrazoleYield 49.1%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 312751,4-DioxaneSolvent

Procedure

A mixture of 1-(4-fluorophenyl)-5-[4-(methylthio)-phenyl]pyrazol-3-amine (3 g), cupric chloride (1.6 g) and t-butyl nitrite (1.14 g) in acetonitrile (50 ml) and dioxane (20 ml) was stirred at ambient temperature for 4 hours. The insoluble was filtered, and to the filtrate were added ethyl acetate and water. The organic layer was separated, washed with dilute hydrochloric acid, dried and concentrated. The oily residue (3.8 g) was purified by column chromatography on silica gel (40 g) eluting with a mixture of toluene and ethyl acetate (10:1) to give a brown oil of 1-(4-fluorophenyl)-5-[4-(methylthio)phenyl]-pyrazole (1.4 g).

Workup

  1. filtrationThe insoluble was filtered
  2. additionto the filtrate were added ethyl acetate and water
  3. customThe organic layer was separated
  4. washwashed with dilute hydrochloric acid
  5. customdried
  6. concentrationconcentrated
  7. customThe oily residue (3.8 g) was purified by column chromatography on silica gel (40 g)
  8. washeluting with a mixture of toluene and ethyl acetate (10:1)

Sources & evidence

ORD record
ord-0fe8a8890cf64859b4738a17b258a42a
Source dataset
uspto-grants-1992_07
Patent number
US05134142

Reaction notes

Loading…