Nitrogen → 1-bromo-4-(phenylethynyl)benzene

HRID 1910102Notes

Reaction equation

HRID 1910102 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.N#N.[C:11]1([C:17]#[CH:18])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1>C(N(CC)CC)C.O1CCCC1.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:11]1([C:17]#[C:18][C:5]2[CH:6]=[CH:7][C:2]([Br:1])=[CH:3][CH:4]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

8

Reactant 3

HCID 947NitrogenHCID 10821PhenylacetyleneHCID 115221-Bromo-4-iodobenzene

Product 1

HCID 2908881-bromo-4-(phenylethynyl)benzeneYield 99.2%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

1-Bromo-4-iodobenzene (20.0 g, 70.7 mmol), bis(triphenylphospine)palladium(II) dichloride (PdCl2(PPh3)2) (250 mg), and CuI (68 mg) were suspended in 50 mL triethylamine (NEt3) and 100 mL tetrahydrofuran (THF). The suspension was treated with 3 cycles of evacuation and refilling with N2. Phenylacetylene (7.21 g, 7.75 mL, 1.0 eq) was added in 0.5 mL portions every 5 minutes to the stirred suspension. The solution was then stirred at room temperature for 22 hours. The solvents were then evaporated. Methylene chloride (100 mL) and 1 M HCl (aqueous) (50 mL) were added, the organic layer was retained, and then was washed again with 1 M HCl (aqueous) (50 mL) and 2×50 mL water, dried (MgSO4), filtered, and the solvent evaporated in vacuum to give 18 g of the title compound as a yellow solid, which was used without further purification.

Workup

  1. customThe solvents were then evaporated
  2. additionMethylene chloride (100 mL) and 1 M HCl (aqueous) (50 mL) were added
  3. washwas washed again with 1 M HCl (aqueous) (50 mL) and 2×50 mL water
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. customthe solvent evaporated in vacuum

Sources & evidence

ORD record
ord-7bc49786ba7d4c66903f0e1fb8f86fad
Source dataset
uspto-grants-2013_12
Patent number
US08599673B2

Reaction notes

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