3-Bromopyridine → 5-Carbomethoxy-8-(3-pyridyl)-oct-7-enenitrile

HRID 1494090Notes

Reaction equation

HRID 1494090 reaction equation
[C:1]([CH:5]([CH2:11][CH:12]=[CH2:13])[CH2:6][CH2:7][CH2:8][C:9]#[N:10])([O:3][CH3:4])=[O:2].Br[C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)C.C(N(CC)CC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([CH:5]([CH2:11][CH:12]=[CH:13][C:15]1[CH:16]=[N:17][CH:18]=[CH:19][CH:20]=1)[CH2:6][CH2:7][CH2:8][C:9]#[N:10])([O:3][CH3:4])=[O:2]

Participants

7

Reactant 3

HCID 122863-BromopyridineHCID 80271Tri-o-tolylphosphineHCID 149867035-Carbomethoxy-oct-7-enenitrile

Product 1

HCID 543965835-Carbomethoxy-8-(3-pyridyl)-oct-7-enenitrile

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalyst2×HCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Procedure

A mixture of 23.5 g of 5-carbomethoxy-oct-7-enenitrile, 20.07 g of 3-bromopyridine and 0.79 g of tri-o-tolylphosphine in 200 mL of 2:1 acetonitrile and triethylamine is stirred at room temperature under nitrogen for one half hour. Palladium acetate (0.27 g) is added and the mixture is stirred under reflux for 40 hours. An additional 0.13 g of palladium acetate is added and the reaction mixture is further heated under reflux for 20 hours. The reaction mixture is evaporated to dryness and the residue is taken up in ethyl acetate. The ethyl acetate solution is washed with water, and then with 3N hydrochloric acid. The acid extract is washed with ethyl acetate, made basic to pH 8-9 with ammonium hydroxide solution and reextracted with ethyl acetate. The ethyl acetate extract is dried and evaporated to dryness to yield 5-carbomethoxy-8-(3-pyridyl)-oct-7-enenitrile.

Workup

  1. stirringthe mixture is stirred
  2. temperatureunder reflux for 40 hours
  3. temperaturethe reaction mixture is further heated
  4. temperatureunder reflux for 20 hours
  5. customThe reaction mixture is evaporated to dryness
  6. washThe ethyl acetate solution is washed with water
  7. extractionThe acid extract
  8. washis washed with ethyl acetate
  9. extractionThe ethyl acetate extract
  10. customis dried
  11. customevaporated to dryness

Sources & evidence

ORD record
ord-c04e95ceaa614722ac2ae384cfc8faff
Source dataset
uspto-grants-1991_06
Patent number
US05025025

Reaction notes

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