P-Cresol → 4-Methylphenyl 2,4,5-trifluorobenzoate

HRID 2359288Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2359288
S(Cl)(Cl)=O.[F:5][C:6]1[CH:14]=[C:13]([F:15])[C:12]([F:16])=[CH:11][C:7]=1[C:8]([OH:10])=[O:9].[CH3:17][C:18]1[CH:23]=[CH:22][C:21](O)=[CH:20][CH:19]=1.C(N(CC)CC)C>C(Cl)Cl>[F:5][C:6]1[CH:14]=[C:13]([F:15])[C:12]([F:16])=[CH:11][C:7]=1[C:8]([O:10][C:21]1[CH:22]=[CH:23][C:18]([CH3:17])=[CH:19][CH:20]=1)=[O:9]

Komponenten

6

Edukt 4

HCID 2879P-CresolHCID 8471TriethylamineHCID 24386Thionyl ChlorideHCID 5211702,4,5-Trifluorobenzoic acid

Produkt 1

HCID 580424084-Methylphenyl 2,4,5-trifluorobenzoateAusbeute 66,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
55 °C

Versuchsvorschrift

Thionyl chloride (50 mL, 680 mmol) was added to 2,4,5-trifluorobenzoic acid (10 g, 57 mmol) and the mixture stirred at 55° C. for 18 hours. After cooling, the excess thionyl chloride was removed in vacuo. The resulting crude oil was azeotroped twice with DCM (30 mL) and toluene (20 mL) and the residue redissolved in DCM (50 mL), then cooled to 0° C. with an ice bath. A mixture of 4-methylphenol (6.4 g, 59 mmol) and triethylamine (10 mL, 71 mmol) in DCM (20 mL) was added over 30 minutes. The reaction was allowed to warm up to room temperature over 1 hour. The crude reaction mixture was partitioned between EtOAc (200 mL) and saturated sodium bicarbonate solution (70 mL). The aqueous layer was separated and extracted with EtOAc (100 mL). The combined organic extracts were combined, washed with saturated sodium bicarbonate solution (70 mL) and water (100 mL), dried over magnesium sulfate and concentrated in vacuo to provide a crude solid, which was purified by silica gel chromatography eluting with 5% EtOAc in heptane to provide the title compound (10.08 g, 66%) as a white solid.

Aufarbeitung

  1. temperatureAfter cooling
  2. customthe excess thionyl chloride was removed in vacuo
  3. customThe resulting crude oil was azeotroped twice with DCM (30 mL) and toluene (20 mL)
  4. dissolutionthe residue redissolved in DCM (50 mL)
  5. temperaturecooled to 0° C. with an ice bath
  6. additionwas added over 30 minutes
  7. temperatureto warm up to room temperature over 1 hour
  8. customThe crude reaction mixture
  9. customwas partitioned between EtOAc (200 mL) and saturated sodium bicarbonate solution (70 mL)
  10. customThe aqueous layer was separated
  11. extractionextracted with EtOAc (100 mL)
  12. washwashed with saturated sodium bicarbonate solution (70 mL) and water (100 mL)
  13. dry with materialdried over magnesium sulfate
  14. concentrationconcentrated in vacuo
  15. customto provide a crude solid, which
  16. customwas purified by silica gel chromatography
  17. washeluting with 5% EtOAc in heptane

Quellen und Nachweise

ORD-Eintrag
ord-23bc6e40bbd346c4917fbb9d6c8a2ba8
Quelldatensatz
uspto-grants-2014_04
Patentnummer
US08685977B2

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