4-Fluoroaniline → Picolinafen

HRID 566583

Reaction equation

HRID 566583 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][C:9]2[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=2)[N:3]=1.[F:19][C:20]1[CH:26]=[CH:25][C:23]([NH2:24])=[CH:22][CH:21]=1.[C:27](=O)([O-])[O-:28].[Na+].[Na+]>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2[C-](C(P(C(C)(C)C)C(C)(C)C)C)C=CC=2)C=CC=CC=1.[CH-]1C=CC=C1.[Fe+2]>[F:19][C:20]1[CH:26]=[CH:25][C:23]([NH:24][C:27]([C:2]2[CH:7]=[CH:6][CH:5]=[C:4]([O:8][C:9]3[CH:14]=[CH:13][CH:12]=[C:11]([C:15]([F:18])([F:17])[F:16])[CH:10]=3)[N:3]=2)=[O:28])=[CH:22][CH:21]=1

Participants

7

Reactant 3

HCID 97314-FluoroanilineHCID 10340Sodium CarbonateHCID 110111722-Chloro-6-[3-(trifluoromethyl)phenoxy]pyridine

Product 1

HCID 3294375Picolinafen

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 76007372(+/-)-1-[2-(Diphenylphosphino)ferrocenyl]ethyl-di-tert-butylphosphineCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
150 °C

Procedure

6.84 g (25 mmol) of 2-chloro-6-[3-(trifluoromethyl)phenoxy]pyridine (content 99.5 percent, prepared according to Example 1), 3.33 g (30 mmol) of 4-fluoroaniline, 2.92 g (27.5 mmol) of sodium carbonate, 2.8 mg (12.5 μmol) of palladium(II) acetate and 68 mg (125 μmol) of (±)-1-[2-(diphenylphosphino)ferrocenyl]ethyl-di-tert-butylphosphine (IVa, R8=methyl, R9=R10=tert-butyl, R11=R12=phenyl) in 25 ml of acetonitrile were placed in an autoclave at room temperature. The autoclave was flushed with inert gas, carbon monoxide was then introduced under a pressure of 5 bar and the temperature was raised to 150° C., the pressure increasing to 7.6 bar. The mixture was stirred for 4 hours at 150° C. After cooling to room temperature and depressurization, the solvent was distilled off and the residue was taken up at 80° C. with 90 ml of methylcyclohexane. The resultant suspension was filtered and the filter cake was rinsed with 10 ml of warm methylcyclohexane. The product crystallized out when the filtrate was cooled to 5° C. The yield of the title compound was 8.11 g (86.2 percent) of a light beige solid. The melting point of the title compound was 104.5°-105.2° C.

Workup

  1. customwere placed in an autoclave at room temperature
  2. customThe autoclave was flushed with inert gas, carbon monoxide
  3. additionwas then introduced under a pressure of 5 bar
  4. temperaturethe pressure increasing to 7.6 bar
  5. temperatureAfter cooling to room temperature
  6. distillationdepressurization, the solvent was distilled off
  7. customwas taken up at 80° C. with 90 ml of methylcyclohexane
  8. filtrationThe resultant suspension was filtered
  9. washthe filter cake was rinsed with 10 ml of warm methylcyclohexane
  10. customThe product crystallized out when the filtrate
  11. temperaturewas cooled to 5° C
  12. customwas 104.5°-105.2° C.

Sources & evidence

ORD record
ord-ff61f3c637bc4200b8bb551f8492d71c
Source dataset
uspto-grants-2001_01
Patent number
US06175011B1

Linked notes

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