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

HRID 234874Notes

Reaction equation

HRID 234874 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.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu](I)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

7

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 3

HCID 83717Copper iodideCatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

1 g of bis(triphenylphosphine)-palladium(II)-chloride, 3.8 g of copper(II)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 heated to the reflux temperature, after which 43.4 g of 3-butynol were added dropwise in the course of 20 minutes at this temperature (about 100° C.). Stirring was continued for a further 5 hours at this temperature. After cooling, the triethylamine was distilled off. The residue was taken up in methyl tertbutyl 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 1N hydrochloric acid and with 10% strength sodium bicarbonate solution and was dried over sodium sulfate. After removal of the solvent, the crude product was distilled under greatly reduced pressure. Yield: 86%.

Workup

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

Sources & evidence

ORD record
ord-62f202c0015d48d4bf019b80b7a4e265
Source dataset
uspto-grants-1997_01
Patent number
US05597776

Reaction notes

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