Phenylacetylene → 4-(2-phenylethynyl)aniline

HRID 533581Notes

Reaction equation

HRID 533581 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.[C:9]1([C:15]#[CH:16])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.C(N(CC)CC)C>[C:9]1([C:15]#[C:16][C:2]2[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

8

Reactant 3

HCID 10821PhenylacetyleneHCID 108934-IodoanilineHCID 11776Triphenylphosphine

Product 1

HCID 46172694-(2-phenylethynyl)aniline

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

More particularly, 4-iodoaniline (17.38 g), phenyl acetylene (10.4 g), and triphenyl phosphine (193 mg) are added to a three-necked 500 mL flask, which is fitted with a reflux condenser, nitrogen blanket, and an overhead mechanical stirrer. Bis(triphenylphosphine)-palladium (II) dichloride (“Pd(PPH3)2Cl2]”) (94 mg) and CuI (38 mg) are then added with 100 mL of triethylamine (“Et3N”). The flask is maintained at room temperature overnight under a nitrogen atmosphere. Afterwards, the reaction mixture is cooled and filtered to remove the precipitate. The precipitate is washed with methylene chloride and the soluble portions are recombined with the filtrate. The solvent is then evaporated to yield 4-phenylethynyl aniline (“Compound E”) as a yellowish solid. Further purification, typically involves repeated re-crystallization from hexanes to give the final product as a pale yellow colored solid.

Workup

  1. customwhich is fitted with a reflux condenser
  2. temperatureAfterwards, the reaction mixture is cooled
  3. filtrationfiltered
  4. customto remove the precipitate
  5. washThe precipitate is washed with methylene chloride
  6. customThe solvent is then evaporated

Sources & evidence

ORD record
ord-964e32c8b40946aebb564f6af11d4f90
Source dataset
uspto-grants-2014_10
Patent number
US08853342B2

Reaction notes

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