Carbon Dioxide → Diphenyl(trifluoromethyl)phosphane

HRID 1085320

Reaktionsgleichung

Reaktionsgleichung von HRID 1085320
Cl[P:2]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C(=O)=O.Br[C:19]([F:22])([F:21])[F:20].C(N(CC)P(N(CC)CC)N(CC)CC)C>CC(C)=O.ClCCl>[C:3]1([P:2]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[C:19]([F:22])([F:21])[F:20])[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1

Komponenten

7

Edukt 4

HCID 280Carbon DioxideHCID 6384BromotrifluoromethaneHCID 66180ChlorodiphenylphosphineHCID 75292Hexaethylphosphorous triamide

Produkt 1

HCID 12487824Diphenyl(trifluoromethyl)phosphaneAusbeute 68 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 180AcetoneLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

A flask equipped with a dry ice condenser was flame dried under a nitrogen stream, and charged with 3.1 mL (17 mmol) of chlorodiphenylphosphine and 10 mL of dichloromethane. After cooling the resulting solution to -78° C. and charging the condenser with dry ice and acetone, 4 mL (43 mmol) of bromotrifluoromethane (Freon 13B1) that had been condensed into a graduated tube was warmed to room temperature and allowed to distill into the flask. The cold solution was treated dropwise with 7 mL (26 mmol) of hexaethylphosphorous triamide, allowed to stir at "78° C. for 1 hour, and allowed to stir at room temperature overnight. Dilution with 50 mL of dichloromethane, water washing (three 50 mL portions), drying (MgSO4), and concentration afforded a brown liquid which was purified by flash chromatography on 50g of silica gel (230-400 mesh) eluted with petroleum ether to give 2.9g (68% yield) of diphenyltrifluoromethylphosphine as a colorless liquid. 19F NMR (CDCl3, relative to CFCl3) -55.60 ppm (d, JPF =73 Hz); 31P NMR (CDCl3, relative to H3PO4) 3.11 ppm (quartet of pentets, JPF =73 Hz, JPH =8 Hz); mass spectrum (70 eV) m/z (relative intensity) 254 (41, M+), 185 (74), 183 (100), 127 (23), 107 (40), 77 (26), 69 (65), 51 (54).

Aufarbeitung

  1. customA flask equipped with a dry ice condenser
  2. temperaturewas flame
  3. customdried under a nitrogen stream
  4. customcondensed into a graduated tube
  5. temperaturewas warmed to room temperature
  6. distillationto distill into the flask
  7. stirringto stir at room temperature overnight
  8. dry with materialDilution with 50 mL of dichloromethane, water washing (three 50 mL portions), drying
  9. concentration(MgSO4), and concentration
  10. customafforded a brown liquid which
  11. customwas purified by flash chromatography on 50g of silica gel (230-400 mesh)
  12. washeluted with petroleum ether

Quellen und Nachweise

ORD-Eintrag
ord-d0f5512724e844d2803019c8d24feb58
Quelldatensatz
uspto-grants-1991_04
Patentnummer
US05008417

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