4-Fluoroaniline → Picolinafen

HRID 1075414Notes

Reaction equation

HRID 1075414 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+].COC1C=CC(P(C2C=CC(OC)=CC=2)C2C=CC(OC)=CC=2)=CC=1>CC1CCCCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[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 4

HCID 97314-FluoroanilineHCID 10340Sodium CarbonateHCID 70071Phosphine, tris(4-methoxyphenyl)-HCID 110111722-Chloro-6-[3-(trifluoromethyl)phenoxy]pyridine

Product 1

HCID 3294375Picolinafen

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 7962MethylcyclohexaneSolvent2×

Conditions

Temperature
80 °C

Procedure

Analogously to Example 4, 6.84 g (25 mmol) of 2-chloro-6-[3-(trifluoromethyl)phenoxy]pyridine, 3.33 g (30 mmol) of 4-fluoroaniline, 2.92 g (27.5 mmol) of sodium carbonate, 5.6 mg (25 μmol) of palladium(II) acetate and 260 mg (0.75 mmol) of tris(4-methoxyphenyl)phosphine in 25 ml of methylcyclohexane were reacted under a CO pressure of 7.5 bar for 20 hours. After cooling to 80° C., the reaction mixture was diluted with 65 ml of warm methylcyclohexane. The salts were filtered off and washed with 10 ml of warm methylcyclohexane. On cooling to 5° C. the product crystallized. The yield was 8.1 g (86 percent) of a light beige solid. The melting point was 104.5° to 105.1° C.

Workup

  1. filtrationThe salts were filtered off
  2. washwashed with 10 ml of warm methylcyclohexane
  3. temperatureOn cooling to 5° C. the product
  4. customcrystallized

Sources & evidence

ORD record
ord-5a6da498c5d448ba87eb62ccdf88b29b
Source dataset
uspto-grants-1999_05
Patent number
US05900484

Reaction notes

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