Triphenylphosphine → HCID 11290100, compound

HRID 380714Notes

Reaction equation

HRID 380714 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([F:9])=[CH:5][CH:4]=1)#[CH:2].Br[C:11]1[CH:12]=[C:13]([CH:23]=[CH:24][CH:25]=1)[C:14]([C:16]1[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=1)=[O:15].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C>[F:9][C:6]1[CH:7]=[CH:8][C:3]([C:1]#[C:2][C:24]2[CH:25]=[CH:11][CH:12]=[C:13]([C:14](=[O:15])[C:16]3[CH:17]=[CH:18][C:19]([F:22])=[CH:20][CH:21]=3)[CH:23]=2)=[CH:4][CH:5]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 5226271-Ethynyl-4-fluorobenzeneHCID 36501933-Bromo-4'-fluorobenzophenone

Product 1

HCID 11290100HCID 11290100, compound

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Conditions

Temperature
80 °C

Procedure

In a 250-mL three-neck, round-bottom flask equipped with a magnetic stirrer, a thermocouple, and a condenser were placed 5.00 g (0.04 Mol) of 1-ethynyl-4-fluorobenzene, 11.16 g (0.04 Mol) of 3-bromo-4′-fluorobenzophenone (from the first step), 0.1 g of triphenylphosphine, 0.05 g of cuprous iodide, 0.05 g of dichlorobis(triphenylphosphine)palladium[II], and 200 mL of de-aerated triethylamine. The reaction mixture was heated to 80° C. with stirring under argon for 4 hr and then cooled to ambient with stirring for an additional 16 hr (overnight). The reaction slurry was filtered to remove the white precipitate of triethylamine hydrobromide. The triethylamine solvent was evaporated and the solid was dissolved in dichloromethane. The resulting solution was washed with water (2×100 mL), 2% HCl (2×100 mL), brine and then dried over sodium sulfate. After filtration and removal of the solvent, the product was purified by crystallization from acetone yielding 23 g (75%)of white crystals having a melting point of 130-131° C. In an alternative experiment, during which recrystallization was carried out in toluene, the recovered pure rhombic needles of the product had a melting point of 135-136° C.

Workup

  1. customIn a 250-mL three-neck, round-bottom flask equipped with a magnetic stirrer
  2. temperaturecooled
  3. stirringwith stirring for an additional 16 hr (overnight)
  4. filtrationThe reaction slurry was filtered
  5. customto remove the white precipitate of triethylamine hydrobromide
  6. customThe triethylamine solvent was evaporated
  7. dissolutionthe solid was dissolved in dichloromethane
  8. washThe resulting solution was washed with water (2×100 mL), 2% HCl (2×100 mL), brine
  9. dry with materialdried over sodium sulfate
  10. filtrationAfter filtration and removal of the solvent
  11. customthe product was purified by crystallization from acetone yielding 23 g (75%)of white crystals
  12. customIn an alternative experiment, during which recrystallization

Sources & evidence

ORD record
ord-50dd5fe01fb24c96aeafefda7d65d6f3
Source dataset
uspto-grants-2001_10
Patent number
US06303733B1

Reaction notes

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