3-Bromopyridine → 6-(Pyridin-3-YL)hex-5-YN-1-OL

HRID 1656312Notes

Reaction equation

HRID 1656312 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[CH2:8]([OH:14])[CH2:9][CH2:10][CH2:11][C:12]#[CH:13]>C(N(CC)CC)C.ClCCl.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:13]#[C:12][CH2:11][CH2:10][CH2:9][CH2:8][OH:14])[CH:3]=1

Participants

6

Reactant 2

HCID 122863-BromopyridineHCID 702345-Hexyn-1-ol

Product 1

HCID 135575516-(Pyridin-3-YL)hex-5-YN-1-OLYield 76.5%

Reagents, catalysts & solvents 3

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

A solution of 45 ml (0.47 mol) of 3-bromopyridine and 52 g (0.53 mol) of 5-hexyn-l-ol in 150 ml of triethylamine and 500 ml of dichloromethane is degassed for 15 minutes with argon, and 3 g (4,3 mmol) of bis(triphenylphosphine)palladium(II)chloride and 450 mg of cuprous iodide is added. The mixture is heated at reflux for 3 h. The cooled reaction mixture is diluted with 1 liter of dichloromethane and is washed with water and brine, dried (K2CO3), concentrated and bulb-to-bulb distilled (b.p. 120°-130° C./0.05 mbar), to give 63 g of 6-(3-pyridyl)hex-5-ynol as a yellow oil, which is dissolved in 500 ml of ethyl acetate and af ter addition of 15 ml of quinoline is hydrogenated f or 5 h over 6 g Lindlar catalyst (Pb-poisoned Pd catalyst) in a Parrhydrogenator. The crude product is evaporatively distilled (b.p. 120°-130° C./0.05 mbar), yielding 61 g (73%) of (Z)-6-(3-pyridyl)hex-5-enol as a colourless viscous liquid. (C11H15NO; F.W. 177.3).

Workup

  1. additionis added
  2. temperatureThe mixture is heated
  3. temperatureat reflux for 3 h
  4. customThe cooled reaction mixture
  5. washis washed with water and brine
  6. dry with materialdried (K2CO3)
  7. concentrationconcentrated
  8. distillationbulb-to-bulb distilled (b.p. 120°-130° C./0.05 mbar)

Sources & evidence

ORD record
ord-3704ea29ebec484f926ac80b5ffdaf03
Source dataset
uspto-grants-1993_10
Patent number
US05254549

Reaction notes

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