Triphenylphosphine → HCID 178447869, compound

HRID 2352471Notes

Reaction equation

HRID 2352471 reaction equation
[CH2:1]([C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2[CH:17]=[CH:16][C:13]([CH:14]=O)=[CH:12][CH:11]=2)[CH2:6][CH2:5]1)[CH2:2][CH3:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Cl[C:38]([F:43])([F:42])C([O-])=O.[Na+]>COCCOCCOC>[CH2:1]([C@H:4]1[CH2:9][CH2:8][C@H:7]([C:10]2[CH:17]=[CH:16][C:13]([CH:14]=[C:38]([F:43])[F:42])=[CH:12][CH:11]=2)[CH2:6][CH2:5]1)[CH2:2][CH3:3]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 2734985Sodium chlorodifluoroacetateHCID 178447881HCID 178447881, compound

Product 1

HCID 178447869HCID 178447869, compoundYield 36.4%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent2×

Procedure

While 4-(trans-4-n-propylcyclohexyl)benzaldehyde (25 g, 0.11 mol), triphenylphosphine (31 g, 0.12 mol) and diethylene glycol dimethyl ether (25 ml) were heated at 160° C. in nitrogen gas current with stirring, a solution of sodium chlorodifluoroacetate (25 g, 0.16 mol) in diethylene glycol dimethyl ether (70 ml) at 70° C. was dropwise added to the above solution over 2 hours, followed by cooling the resulting solution, filtering it by suction, concentrating the filtrate under reduced pressure, distilling the concentrate under reduced pressure (150° C., 3 mmHg), dissolving the distillate in toluene (100 ml), washing the toluene solution three times with 6N-hydrochloric acid (100 ml) and further with water till the washing water became neutral, drying the toluene solution with anhydrous sodium sulfate, separating the drying agent, distilling off toluene, recrystallizing the residue from a mixed solvent of heptane with ethanol (1:5), dissolving the resulting crystals in heptane, purifying the solution according to silica gel column chromatography, again distilling the resulting solution under reduced pressure, three times recrystallizing the residue from a mixed solvent of heptane with ethanol (1:5) and finally drying the resulting crystals to obtain the objective product (10 g, 0.04 mol).

Workup

  1. temperatureby cooling the resulting solution
  2. filtrationfiltering it by suction
  3. concentrationconcentrating the filtrate under reduced pressure
  4. distillationdistilling the
  5. concentrationconcentrate under reduced pressure (150° C., 3 mmHg)
  6. dissolutiondissolving the distillate in toluene (100 ml)
  7. washwashing the toluene solution three times with 6N-hydrochloric acid (100 ml)
  8. dry with materialdrying the toluene solution with anhydrous sodium sulfate
  9. customseparating the drying agent
  10. distillationdistilling off toluene
  11. customrecrystallizing the residue from a mixed solvent of heptane with ethanol (1:5)
  12. dissolutiondissolving the resulting crystals in heptane
  13. custompurifying the solution
  14. distillationagain distilling the resulting solution under reduced pressure, three times
  15. customrecrystallizing the residue from a mixed solvent of heptane with ethanol (1:5)
  16. customfinally drying the resulting crystals

Sources & evidence

ORD record
ord-2a7cc790cdd14504ba2ab51e077fb192
Source dataset
uspto-grants-1989_10
Patent number
US04877548

Reaction notes

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