1-Bromo-4-fluorobenzene → 4-(4-Fluorophenyl)but-3-yn-1-ol

HRID 2395941Notes

Reaction equation

HRID 2395941 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:21]1[CH:26]=[CH:25][C:24]([F:27])=[CH:23][CH:22]=1.[CH2:28]([OH:32])[CH2:29][C:30]#[CH:31]>C(N(CC)CC)C.C(OC)(C)(C)C.O.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>[F:27][C:24]1[CH:25]=[CH:26][C:21]([C:31]#[C:30][CH2:29][CH2:28][OH:32])=[CH:22][CH:23]=1

Participants

9

Reactant 3

HCID 99931-Bromo-4-fluorobenzeneHCID 11776TriphenylphosphineHCID 135663-Butyn-1-OL

Product 1

HCID 124784404-(4-Fluorophenyl)but-3-yn-1-olYield 86%

Reagents, catalysts & solvents 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 8471TriethylamineSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Procedure

1 g of bis-(triphenylphosphine)-palladium(II) chloride, 3.8 g of copper(I) iodide and 8.7 g of triphenylphosphine were added in succession to a solution of 100 g of 4-bromofluorobenzene in 350 ml of triethylamine. The mixture was heated to reflux temperature, after which 43.4 g of 3-butynol were added dropwise in the course of 20 minutes at this temperature (about100° C.). Stirring was carried out for a further 5 hours at this temperature. After the mixture had cooled, the triethylamine was distilledoff. The residue was taken up in methyl tert-butyl ether and water. The aqueous phase was extracted twice more with methyl tert-butyl ether, and the combined organic extracts were washed in succession with 1 N hydrochloric acid and with 10% strength by weight sodium bicarbonate solution and dried over sodium sulfate. After removal of the solvent, the crude product was distilled under greatly reduced pressure. Yield: 86%.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux temperature
  3. temperatureAfter the mixture had cooled
  4. extractionThe aqueous phase was extracted twice more with methyl tert-butyl ether
  5. washthe combined organic extracts were washed in succession with 1 N hydrochloric acid and with 10% strength by weight sodium bicarbonate solution
  6. dry with materialdried over sodium sulfate
  7. customAfter removal of the solvent
  8. distillationthe crude product was distilled under greatly reduced pressure

Sources & evidence

ORD record
ord-d9acc85bdca047c7b337418bf2c35785
Source dataset
uspto-grants-1996_02
Patent number
US05491123

Reaction notes

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