Water → 5-(2-Trifluoromethylphenyl)-4-pentynenitrile

HRID 1779409

Reaction equation

HRID 1779409 reaction equation
[F:1][C:2]([F:11])([F:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1I.[C:12](#[N:17])[CH2:13][CH2:14][C:15]#[CH:16].C(N(CC)CC)C.O>C(#N)C.[Cu](I)I>[F:1][C:2]([F:11])([F:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:16]#[C:15][CH2:14][CH2:13][C:12]#[N:17]

Participants

7

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 67957Benzene, 1-iodo-2-(trifluoromethyl)-HCID 1405604-Cyano-1-butyne

Product 1

HCID 199555385-(2-Trifluoromethylphenyl)-4-pentynenitrileYield 92.9%

Reagents, catalysts & solvents 2

HCID 83717Copper iodideCatalystHCID 6342AcetonitrileSolvent

Procedure

Under a nitrogen atmosphere, a solution of 15.0 grams (0.055 mole) of 2-trifluoromethylphenyl iodide, 4.8 grams (0.061 mole) of 4-pentynenitrile, 30.6 mL (0.22 mole) of triethylamine, 0.4 gram (0.0006 mole) of bis(triphenylphosphine)palladium(11) chloride, and 0.1 gram (0.0006 mole) of copper(11) iodide in 50 mL of acetonitrile was stirred at ambient temperature for 5 hours. After this time, gas chromatographic analysis (GC) of the reaction mixture indicated that the reaction was about 60% complete. The reaction mixture was warmed to 40°-45° C., where it was stirred for 16 hours. After this time the reaction mixture was poured into 300 mL of water, and the mixture was extracted with two 100 mL portions of diethyl ether. The combined extracts were washed with aqueous dilute hydrochloric acid and then were dried with magnesium sulfate. The mixture was filtered and concentrated under reduced pressure to a residual oil. The oil was subjected to column chromatography on silica gel. Elution was accomplished using 1:1 - methylene chloride and petroleum ether. The product-containing fractions were combined and concentrated under reduced pressure, yielding 11.4 grams of 5-(2-trifluoromethylphenyl)-4-pentynenitrile. The NMR spectrum was consistent with the proposed structure.

Workup

  1. temperatureThe reaction mixture was warmed to 40°-45° C.
  2. extractionthe mixture was extracted with two 100 mL portions of diethyl ether
  3. washThe combined extracts were washed with aqueous dilute hydrochloric acid
  4. dry with materialwere dried with magnesium sulfate
  5. filtrationThe mixture was filtered
  6. concentrationconcentrated under reduced pressure to a residual oil
  7. washElution
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-dbd975ee96c041e49c85343f740c2ccb
Source dataset
uspto-grants-1997_05
Patent number
US05627189

Linked notes

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