1-Hexyne → HCID 57225482, compound

HRID 1769274Notes

Reaction equation

HRID 1769274 reaction equation
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH3:6].Cl[C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1>C(NCC)C.[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([C:8]1[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][N:9]=1)#[C:2][CH2:3][CH2:4][CH2:5][CH3:6]

Participants

6

Reactant 2

HCID 127321-HexyneHCID 276852,5-Dichloropyridine

Product 1

HCID 57225482HCID 57225482, compoundYield 87.8%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 8021DiethylamineSolvent

Procedure

9.0 ml (80 mmol) of 1-hexyne and 6.0 g (40 mmol) of 2,5-dichloropyridine in 80 ml of diethylamine are placed under argon, whereby a pale yellow solution results. Thereto there are added 0.40 g (1.5 mmol) of triphenylphosphine, 0.04 g (0.02 mmol) of copper-(I) iodide as well as 0.24 g (0.9 mmol) of palladium-dichloro-bis(triphenylphospine). The orange solution obtained is subsequently heated to reflux for 24 hours while stirring. Thereafter, the reaction mixture is cooled to 25° and evaporated at 40° under reduced pressure. The brown residue is then treated with 50 ml of ethanol and again evaporated. The crude product is filtered over 50 g of silica gel with 700 ml of hexane/toluene (1:1) and the eluate is evaporated at 50° under reduced pressure. The residue is subsequently distilled in a bulb tube at 190°/2600 Pa. There are obtained 6.8 g of 2-hexynyl-5-chloropyridine as a yellow oil.

Workup

  1. customwhereby a pale yellow solution results
  2. customThe orange solution obtained
  3. temperatureis subsequently heated
  4. temperatureto reflux for 24 hours
  5. temperatureThereafter, the reaction mixture is cooled to 25°
  6. customevaporated at 40° under reduced pressure
  7. additionThe brown residue is then treated with 50 ml of ethanol
  8. customagain evaporated
  9. filtrationThe crude product is filtered over 50 g of silica gel with 700 ml of hexane/toluene (1:1)
  10. customthe eluate is evaporated at 50° under reduced pressure
  11. distillationThe residue is subsequently distilled in a bulb tube at 190°/2600 Pa

Sources & evidence

ORD record
ord-95d2ec38f142481a8e424bd079b596ee
Source dataset
uspto-grants-1995_01
Patent number
US05380861

Reaction notes

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