Ethyl Acetate → 5-Vinylnicotinonitrile

HRID 606827

Reaction equation

HRID 606827 reaction equation
[CH2:1]([Sn](CCCC)(CCCC)C=C)[CH2:2]CC.Br[C:17]1[CH:18]=[N:19][CH:20]=[C:21]([CH:24]=1)[C:22]#[N:23].[Cl-].[NH4+].C(OCC)(=O)C>C1(C)C=CC=CC=1.C1(C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)[Pd][P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:1]([C:17]1[CH:18]=[N:19][CH:20]=[C:21]([CH:24]=1)[C:22]#[N:23])=[CH2:2]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 81998TributylvinyltinHCID 7367935-Bromonicotinonitrile

Product 1

HCID 670475755-VinylnicotinonitrileYield 70.3%

Reagents, catalysts & solvents 2

HCID 178419050HCID 178419050, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

Add bis(triphenylphosphine)palladium (II) dichloride (0.460 g, 0.66 mmol) and tributyl-vinyl-stannane (7.2 mL, 24.6 mmol) to a solution of 5-bromonicotinonitrile (3.0 g, 16.4 mmol) in toluene (50 mL) and stir at 110° C. for 150 min. Add an aqueous saturated solution of ammonium chloride and ethyl acetate and separate the layers. Wash the organic layer twice with an aqueous saturated solution of potassium fluoride and once with water. Dry (sodium sulfate), filter, and concentrate. Purify the residue by silica gel chromatography, eluting with 3:1 hexane:ethyl acetate, to give the title compound (1.5 g, 70%).

Workup

  1. customseparate the layers
  2. washWash the organic layer twice with an aqueous saturated solution of potassium fluoride
  3. dry with materialDry (sodium sulfate)
  4. filtrationfilter
  5. concentrationconcentrate
  6. customPurify the residue by silica gel chromatography
  7. washeluting with 3:1 hexane

Sources & evidence

ORD record
ord-56b43414d3494c388f5d80d9389fb119
Source dataset
uspto-grants-2011_03
Patent number
US07915424B2

Linked notes

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