Chloride → 4-(4-Fluorophenyl)but-3-yn-1-ol

HRID 1768540Notes

Reaction equation

HRID 1768540 reaction equation
[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:22]1[CH:27]=[CH:26][C:25]([F:28])=[CH:24][CH:23]=1.[CH2:29]([OH:33])[CH2:30][C:31]#[CH:32]>C(N(CC)CC)C.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[F:28][C:25]1[CH:26]=[CH:27][C:22]([C:32]#[C:31][CH2:30][CH2:29][OH:33])=[CH:23][CH:24]=1

Participants

8

Reactant 4

HCID 312ChlorideHCID 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 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178419050HCID 178419050, 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 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 carried out 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% sodium bicarbonate solution and dried over sodium sulfate. After the solvent had been removed, the crude product was distilled at 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% sodium bicarbonate solution
  6. dry with materialdried over sodium sulfate
  7. customAfter the solvent had been removed
  8. distillationthe crude product was distilled at greatly reduced pressure

Sources & evidence

ORD record
ord-2e5c5b4ccf214739a6422e63c1420041
Source dataset
uspto-grants-1995_01
Patent number
US05378677

Reaction notes

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