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

HRID 1641984Notes

Reaction equation

HRID 1641984 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-necked 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 placed with nitrogen, 200 mL of tetrahydrofuran (THF) and 9.0 mL of triethylamine (Et3N) were added to 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 nitrogen stream at room temperature for 20 hours. After a predetermined time, a 3% hydrochloric acid was added to the mixture, and an aqueous layer and an organic layer were separated in the mixture. Then, an organic substance was extracted with ethyl acetate from the aqueous layer. The obtained extract was washed with a saturated aqueous sodium chloride solution together with the organic layer and then dried over 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 condensed to obtain a solid. The obtained solid was recrystallized with hexane, so that, 7.41 g of target light-brown powder was obtained with a yield of 55%.

Workup

  1. customIn a 500 mL three-necked flask were placed
  2. additionwere added to the flask
  3. customthe mixture was degassed
  4. stirringthe mixture was stirred under nitrogen stream at room temperature for 20 hours
  5. customan aqueous layer and an organic layer were separated in the mixture
  6. extractionThen, an organic substance was extracted with ethyl acetate from the aqueous layer
  7. extractionThe obtained extract
  8. washwas washed with a saturated aqueous sodium chloride solution together with the organic layer
  9. dry with materialdried over magnesium sulfate
  10. 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
  11. customcondensed
  12. customto obtain a solid
  13. customThe obtained solid was recrystallized with hexane
  14. customso that, 7.41 g of target light-brown powder was obtained with a yield of 55%

Sources & evidence

ORD record
ord-2b17763daab24a34aded141c7b4c1e12
Source dataset
uspto-grants-2012_02
Patent number
US08119259B2

Reaction notes

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