3-Bromopyridine → 6-(3-Pyridinyl)-5-hexynenitrile

HRID 1583437Notes

Reaction equation

HRID 1583437 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[C:8](#[N:14])[CH2:9][CH2:10][CH2:11][C:12]#[CH:13]>ClCCl.C(N(CC)CC)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[N:4]1[CH:5]=[CH:6][CH:7]=[C:2]([C:13]#[C:12][CH2:11][CH2:10][CH2:9][C:8]#[N:14])[CH:3]=1

Participants

6

Reactant 2

HCID 122863-BromopyridineHCID 1398525-Hexynenitrile

Product 1

HCID 137397376-(3-Pyridinyl)-5-hexynenitrileYield 79%

Reagents, catalysts & solvents 3

HCID 178418476HCID 178418476, compoundCatalystHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

Argon was passed through a solution of 45 ml of 3-bromopyridine and 49.61 g of 5-hexynenitrile in 500 ml of dichloromethane and 150 ml of dry triethylamine for 15 minutes and 3.0 g of bis(triphenylphosphine)palladium dichloride and 0.45 g of cuprous iodide were added. The reaction flask was evacuated and refilled with argon and was heated to reflux for 12 hours. The resulting mixture was diluted with 1 L of dichloromethane and washed with 2×300 ml of water, 1×300 ml brine, dried over potassium carbonate and concentrated. The residue was distilled to afford 62.82 g (79%) of 6-(3-pyridinyl)-5-hexynenitrile as a yellow oil, bp 140°-170° C./0.2 mm., suitable for use in the next step. A portion was purified by chromatography over silica gel eluting with 1:1 ethyl acetate-hexane containing 1% triethylamine and was redistilled to give an analytical sample of 6-(3-pyridinyl)-5-hexynenitrile.

Workup

  1. customThe reaction flask was evacuated
  2. additionrefilled with argon
  3. temperaturewas heated
  4. temperatureto reflux for 12 hours
  5. additionThe resulting mixture was diluted with 1 L of dichloromethane
  6. washwashed with 2×300 ml of water, 1×300 ml brine
  7. dry with materialdried over potassium carbonate
  8. concentrationconcentrated
  9. distillationThe residue was distilled

Sources & evidence

ORD record
ord-1873507ddc764f25be479929d421b221
Source dataset
uspto-grants-1985_11
Patent number
US04551460

Reaction notes

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