3-Bromopyridine → HCID 54396583, compound

HRID 465545Notes

Reaction equation

HRID 465545 reaction equation
[CH3:1][O:2][C:3]([CH:5]([CH2:11][CH:12]=[CH2:13])[CH2:6][CH2:7][CH2:8][C:9]#[N:10])=[O:4].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>[CH3:1][O:2][C:3]([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:4]

Participants

6

Reactant 3

HCID 122863-BromopyridineHCID 80271Tri-o-tolylphosphineHCID 14986703HCID 14986703, compound

Product 1

HCID 54396583HCID 54396583, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalyst2×HCID 21895542Acetonitrile triethylamineSolvent

Procedure

A mixture of 23.5 g of 5-methoxycarbonyl-oct-7-enenitrile, 20.07 g of 3-bromopyridine and 0.79 g of tri-o-tolylphosphine in 200 ml of 2:1 acetonitrile/triethylamine is stirred at room temperature under nitrogen for 0.5 h. Palladium acetate (0.27 g) is added and the mixture is stirred under reflux for 40 h. An additional 0.13 g of palladium acetate is added and the reaction mixture is further heated under reflux for 20 h. 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 aqueous ammonia and reextracted with ethyl acetate. The ethyl acetate extract is dried and evaporated to dryness to yield 5-methoxycarbonyl-8-(3-pyridyl)-oct-7-enenitrile.

Workup

  1. stirringthe mixture is stirred
  2. temperatureunder reflux for 40 h
  3. temperaturethe reaction mixture is further heated
  4. temperatureunder reflux for 20 h
  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-c1e21ede853e474e86e144ed0882bb50
Source dataset
uspto-grants-1992_10
Patent number
US05153214

Reaction notes

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