Carbon Dioxide → Diphenyl(trifluoromethyl)phosphane

HRID 1085320

反応式

HRID 1085320 の反応式
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

参加物

7

反応物 4

HCID 280Carbon DioxideHCID 6384BromotrifluoromethaneHCID 66180ChlorodiphenylphosphineHCID 75292Hexaethylphosphorous triamide

生成物 1

HCID 12487824Diphenyl(trifluoromethyl)phosphane収率 68%

試薬・触媒・溶媒 2

HCID 180Acetone溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
-78 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-d0f5512724e844d2803019c8d24feb58
出典データセット
uspto-grants-1991_04
特許番号
US05008417

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