Dichloromethane → 4-(Perfluoro3-iodopropyl)phenyl acetate

HRID 1391354Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1391354
[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8](I)=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[I:12][C:13]([F:22])([F:21])[C:14]([F:20])([F:19])[C:15]([F:18])([F:17])I.[Cl-].[NH4+].C(Cl)Cl>CS(C)=O.[Cu]>[C:1]([O:4][C:5]1[CH:10]=[CH:9][C:8]([C:15]([F:18])([F:17])[C:14]([F:20])([F:19])[C:13]([F:22])([F:21])[I:12])=[CH:7][CH:6]=1)(=[O:3])[CH3:2]

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 25517Ammonium ChlorideHCID 1417934-IodophenylacetateHCID 109164621,1,2,2,3,3-Hexafluoro-1,3-diiodopropane

Produkt 1

HCID 213310104-(Perfluoro3-iodopropyl)phenyl acetateAusbeute 57,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23978CopperKatalysator2×HCID 679Dimethyl SulfoxideLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

A solution of p-iodophenyl acetate (27.5 g, 105 mmol) and 1,3-diiodohexafluoropropane (52.0g, 128.7 mmol) in 100 ml of anhydrous dimethyl sulfoxide was heated to 120° C. under nitrogen. Copper powder (13.5 g, 211 g atoms) was added to the vigorously stirred solution in five approximately equal amounts at 20 minute intervals. After the addition of copper was complete, the reaction mixture was stirred at 120° C. for an additional 1.5 hours. On cooling, saturated aqueous ammonium chloride together with methylene chloride was added to the reaction vessel. The excess copper and cuprous salts were filtered off, the organic layer separated, and the aqueous layer was extracted with more methylene chloride. The organic extracts were combined, washed well with water, dried over anhydrous magnesium sulfate, and reduced in volume to a light yellow oil. The oil was refluxed in 25 ml of acetic anhydride for 45 minutes and the excess acetic anhydride and acetic acid were vacuum distilled. Distillation of the residual oil yielded 24.85 g of crude 4-(perfluoro-3-iodopropyl)phenyl acetate bp126°-127° C./3.4 mm Hg, mp 75°-81° C. Recrystallization of this material from hexane gave 20.8 g (48% yield) of purer material, mp 84.5°-88° C. Repeated crystallization from hexane raised the melting point to 88.5°-89.5° C., which could not be improved upon by further recrystallization.

Aufarbeitung

  1. temperatureOn cooling
  2. filtrationThe excess copper and cuprous salts were filtered off
  3. customthe organic layer separated
  4. extractionthe aqueous layer was extracted with more methylene chloride
  5. washwashed well with water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. temperatureThe oil was refluxed in 25 ml of acetic anhydride for 45 minutes
  8. distillationdistilled
  9. distillationDistillation of the residual oil

Quellen und Nachweise

ORD-Eintrag
ord-0d641aac58114179a44835d4a7f67f55
Quelldatensatz
uspto-grants-1979_02
Patentnummer
US04142037

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