Hydrochloric Acid → 1-bromo-4-(phenylethynyl)benzene

HRID 2408216Notes

Reaction equation

HRID 2408216 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[C:9]1([C:15]#[CH:16])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.O1CCCC1.Cl>[Cu]I.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.C(N(CC)CC)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:16]#[C:15][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 10821PhenylacetyleneHCID 115221-Bromo-4-iodobenzene

Product 1

HCID 2908881-bromo-4-(phenylethynyl)benzene

Reagents, catalysts & solvents 3

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

Procedure

In a 500-mL three-neck flask were placed 14 g (51 mmol) of p-bromoiodobenzene, 5.2 g (52 mmol) of phenylacetylene, and 98 mg (0.50 mmol) of copper(I) iodide. After the atmosphere in the flask was replaced with nitrogen, 200 mL of tetrahydrofuran and 9.0 mL of triethylamine were placed in the flask, and the mixture was degassed by being stirred under reduced pressure. To this mixture was added 0.34 mg (0.50 mmol) of bis(triphenylphosphine)palladium(II) dichloride, and the mixture was stirred under a nitrogen stream at room temperature for 20 hours. After a predetermined time, 3% hydrochloric acid was added to the mixture, and an organic substance was extracted with ethyl acetate from the aqueous phase. The extracted solution combined with the organic phase was washed with brine and dried with magnesium sulfate. The mixture was subjected to suction filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina, and the filtrate was concentrated to give a solid. The obtained solid was recrystallized with hexane; thus, 7.4 g of a light-brown powder which was a product was obtained in a yield of 55%.

Workup

  1. customIn a 500-mL three-neck flask were placed
  2. customthe mixture was degassed
  3. stirringthe mixture was stirred under a nitrogen stream at room temperature for 20 hours
  4. extractionan organic substance was extracted with ethyl acetate from the aqueous phase
  5. washwas washed with brine
  6. dry with materialdried with magnesium sulfate
  7. filtrationThe mixture was subjected to suction filtration through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), and alumina
  8. concentrationthe filtrate was concentrated
  9. customto give a solid
  10. customThe obtained solid was recrystallized with hexane
  11. customwas obtained in a yield of 55%

Sources & evidence

ORD record
ord-2e94347c1d994470bcb7529b481d5586
Source dataset
uspto-grants-2014_08
Patent number
US08815412B2

Reaction notes

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