Triphenylphosphine → HCID 10943735, compound

HRID 1734743Notes

Reaction equation

HRID 1734743 reaction equation
[CH3:1][Si:2]([C:5]#[CH:6])([CH3:4])[CH3:3].Cl[C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cu]I.C(NCC)C>[CH3:1][Si:2]([CH3:4])([CH3:3])[C:5]#[C:6][C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 276852,5-DichloropyridineHCID 66111Trimethylsilylacetylene

Product 1

HCID 10943735HCID 10943735, compoundYield 28.6%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8021DiethylamineSolvent

Procedure

1.2 ml (10 mmol) of trimethylsilylacetylene, 40 ml of diethylamine and 1.5 g (10 mmol) of 2,5-dichloropyridine are stirred at 20° under argon. To the colourless solution obtained there are added 0.1 g (0.4 mmol) of triphenylphosphine, 0.01 g (0.05 mmol) of copper-(I) iodide as well as 0.06 g (0.25 mmol) of palladium-dichloro-bis(acetonitrile). The reaction solution is subsequently heated to reflux for 5 hours while stirring. After cooling to 25° the reaction solution is evaporated at 40° under reduced pressure. 50 ml of ethanol are subsequently added to the residue and the mixture is again evaporated. The crude product is filtered over 30 g of silica gel with ethyl acetate and the eluate is evaporated, whereby 1.6 g of brown liquid remain behind. 1.0 g thereof is distilled in a bulb tube at 70°/0.1 Pa, whereby there are obtained as the main fraction 0.6 g of 2-trimethylsilylethynyl-5-chloropyridine which solidifies upon standing.

Workup

  1. customTo the colourless solution obtained there
  2. temperatureThe reaction solution is subsequently heated
  3. temperatureto reflux for 5 hours
  4. temperatureAfter cooling to 25° the reaction solution
  5. customis evaporated at 40° under reduced pressure
  6. addition50 ml of ethanol are subsequently added to the residue
  7. customthe mixture is again evaporated
  8. filtrationThe crude product is filtered over 30 g of silica gel with ethyl acetate
  9. customthe eluate is evaporated
  10. distillation1.0 g thereof is distilled in a bulb tube at 70°/0.1 Pa, whereby there

Sources & evidence

ORD record
ord-593094ff075146b183b44c147ab58889
Source dataset
uspto-grants-1996_07
Patent number
US05534635

Reaction notes

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