4-Fluoroaniline → Picolinafen

HRID 988838

Reaktionsgleichung

Reaktionsgleichung von HRID 988838
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+].C1(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C(C)=CC=CC=1.[Pd]>[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.[F:18][C:15]([F:16])([F:17])[C:11]1[CH:10]=[C:9]([CH:14]=[CH:13][CH:12]=1)[O:8][C:4]1[CH:5]=[CH:6][CH:7]=[CH:2][N:3]=1

Komponenten

8

Edukt 4

HCID 97314-FluoroanilineHCID 10340Sodium CarbonateHCID 821241,4-Bis(diphenylphosphino)butaneHCID 110111722-Chloro-6-[3-(trifluoromethyl)phenoxy]pyridine

Produkt 2

HCID 3294375PicolinafenAusbeute 92,1 %HCID 225955262-{3-(Trifluoromethyl)phenoxy}pyridineAusbeute 2,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 7237O-XyleneLösungsmittel

Reaktionsbedingungen

Temperatur
200 °C

Versuchsvorschrift

6.84 g (25 mmol) of 2-chloro-6-[3-(trifluoromethyl)phenoxy]pyridine (content 99.5 percent prepared according to Example 1), 4.17 g (37.5 mmol) of 4-fluoroaniline, 2.92 g (27.5 mmol) of sodium carbonate, 0.27 g (0.25 mmol) of palladium/activated charcoal (10 percent Pd) and 0.32 g (0.75 mmol) of 1,4-bis(diphenylphosphino)butane (IV, n=4, R8=R9=R10=R11=phenyl) in 25 ml of xylene 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 200° C. The CO pressure was increased to 14.5 bar and the mixture was stirred for 16 hours at 200° C. After cooling to room temperature and depressurization, the reaction mixture was treated with 50 ml of xylene and 50 ml of water and filtered. The aqueous phase was extracted with 25 ml of xylene and the combined organic phases were washed with 30 ml of water. The composition of the dissolved products was determined by GC. 92.1 percent of the title compound (amide), 1.9 percent of educt and 6.0 percent of by-products (3.1 percent of secondary amine formed by direct substitution of Cl by the aniline, and 2.9 percent of 2-[3-(trifluoromethyl)phenoxy]pyridine formed by hydrogenolysis) were found. After distillation of the solvent, the crude product (8.63 g) was obtained in the form of a yellow solid. The crude product was purified by recrystallization from methylcyclohexane. the yield of the title compound product was 6.3 g (67 percent) of colorless crystals. The melting point of the product was 104° to 105° C. Other data concerning the title compound was:

Aufarbeitung

  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 CO pressure was increased to 14.5 bar
  5. temperatureAfter cooling to room temperature
  6. additiondepressurization, the reaction mixture was treated with 50 ml of xylene and 50 ml of water
  7. filtrationfiltered
  8. extractionThe aqueous phase was extracted with 25 ml of xylene
  9. washthe combined organic phases were washed with 30 ml of water

Quellen und Nachweise

ORD-Eintrag
ord-54ae5f2484be4f76a32c5d0646be1e69
Quelldatensatz
uspto-grants-2003_10
Patentnummer
US06635766B1

Verknüpfte Notizen

Wird geladen…