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

HRID 1492376Notes

Reaction equation

HRID 1492376 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][CH:3]=1.[CH2:9]([OH:13])[CH2:10][C:11]#[CH:12]>C(N(CC)CC)C.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.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]#[C:11][CH2:10][CH2:9][OH:13])=[CH:3][CH:4]=1

Participants

7

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

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. This mixture was refluxed, after which 43.4 g of 3-butynol were added dropwise at this temperature (about 100° C.) in the course of 20 minutes. The mixture was stirred for a further 5 hours at this temperature. After the mixture had cooled, the triethylamine was distilled off. The residue was taken up in methyl tert-butyl ether and water. The aqueous phase was extracted twice with methyl tert-butyl ether, and the combined organic extracts were washed in succession with 1 N hydrochloric acid and with 10% strength sodium bicarbonate solution, dried over sodium sulfate and evaporated down in a rotary evaporator. Distillation under greatly reduced pressure gave 80 g (86%) of the desired compound.

Workup

  1. temperatureThis mixture was refluxed
  2. temperatureAfter the mixture had cooled
  3. distillationthe triethylamine was distilled off
  4. extractionThe aqueous phase was extracted twice with methyl tert-butyl ether
  5. washthe combined organic extracts were washed in succession with 1 N hydrochloric acid and with 10% strength sodium bicarbonate solution
  6. dry with materialdried over sodium sulfate
  7. customevaporated down in a rotary evaporator
  8. distillationDistillation under greatly reduced pressure

Sources & evidence

ORD record
ord-b4ce7587f64545e192f3d406a78f15aa
Source dataset
uspto-grants-1994_12
Patent number
US05374609

Reaction notes

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