Phenylacetylene → 4-(Phenylethynyl)pyridine

HRID 1900704Notes

Reaction equation

HRID 1900704 reaction equation
Cl.Br[C:3]1[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=1.[C:9]1([C:15]#[CH:16])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C(N(CC)CC)C.[Cu]I.C1(P([Pd-](Cl)P(C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:9]1([C:15]#[C:16][C:3]2[CH:8]=[CH:7][N:6]=[CH:5][CH:4]=2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

6

Reactant 2

HCID 10821PhenylacetyleneHCID 881004-Bromopyridinium chloride

Product 1

HCID 3521724-(Phenylethynyl)pyridineYield 31.1%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178479804HCID 178479804, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of 4-bromopyridine hydrochloride (9.75 g, 50 mmol), phenylacetylene (11 ml, 10.2 g; 100 mmol), copper (I) iodide (50 mg) and bis(triphenylphosphino)palladium (II) chloride (200 mg) in dry triethylamine (60 ml) was stirred under reflux for 16 h, the cooled reaction mixture filtered, and the filtrate evaporated. The residual black oil was dissolved in ethyl acetate (100 ml) and washed with saturated aqueous sodium carbonate (2×50 ml) and HCl (1M, 4×25 ml). The acidic washings were extracted with ethyl acetate (2×25 ml) and then basified (5M NaOH). The resulting suspension was extracted with dichloromethane (4×25 ml), the combined organic layers washed with water (25 ml), dried (MgSO4), evaporated, and the residue chromatographed on silica gel, eluting with 7:3 ethyl acetate/60°-80° petrol to give the product as a buff solid (2.79 g, 31%).

Workup

  1. temperatureunder reflux for 16 h
  2. customthe cooled reaction mixture
  3. filtrationfiltered
  4. customthe filtrate evaporated
  5. dissolutionThe residual black oil was dissolved in ethyl acetate (100 ml)
  6. washwashed with saturated aqueous sodium carbonate (2×50 ml) and HCl (1M, 4×25 ml)
  7. extractionThe acidic washings were extracted with ethyl acetate (2×25 ml)
  8. extractionThe resulting suspension was extracted with dichloromethane (4×25 ml)
  9. washthe combined organic layers washed with water (25 ml)
  10. dry with materialdried (MgSO4)
  11. customevaporated
  12. customthe residue chromatographed on silica gel
  13. washeluting with 7:3 ethyl acetate/60°-80° petrol

Sources & evidence

ORD record
ord-9561aedcb92a4cb6bcc351172c6a89f5
Source dataset
uspto-grants-1996_11
Patent number
US05576336

Reaction notes

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