Pyridine → Bicyclo[2.2.2]oct-5-ene-2-carbonitrile, 2-chloro-

HRID 2406875Notes

Reaction equation

HRID 2406875 reaction equation
N1C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)[Cl:8].[C:13]([CH:15]1[CH2:20][CH:19]2[CH2:21][CH2:22][CH:16]1[CH:17]=[CH:18]2)#[N:14]>C(Cl)(Cl)Cl>[Cl:8][C:15]1([C:13]#[N:14])[CH2:20][CH:19]2[CH2:21][CH2:22][CH:16]1[CH:17]=[CH:18]2

Participants

5

Reactant 3

HCID 1049PyridineHCID 24819Phosphorus pentachlorideHCID 137792Bicyclo[2.2.2]oct-5-ene-2-carbonitrile

Product 1

HCID 243827Bicyclo[2.2.2]oct-5-ene-2-carbonitrile, 2-chloro-Yield 95%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

To a refluxing mixture of pyridine (14.2 g, 0.180 mol), phosphorus pentachloride (28.0 g, 0.135 mol), and chloroform (100 mL) was added drop-wise a solution of 5-cyanobicyclo[2,2,2]oct-2-ene (12 g, 90 mmol) in chloroform (50 mL). The resulting mixture was heated at reflux for 15 h, cooled, and poured onto ice. The organic layer was concentrated, and the residue was purified by chromatography on silica gel, eluting with mixtures of ethyl acetate (0.5% to 1%) in petroleum ether, to give 5-chloro-5-cyanobicyclo[2,2,2]oct-2-ene (14.3 g, 95% yield) as a white semisolid, 1H NMR (300 MHz, CDCl3) δ 1.3-1.5 (m, 3H), 2.02-2.18 (m, 2H), 2.51 (m, 1H), 2.72 (m, 1H), 3.12 (m, 1H), 6.22 (m, 1H), 6.41 (m, 1H); GCMS (m/z); 167.

Workup

  1. temperatureThe resulting mixture was heated
  2. temperatureat reflux for 15 h
  3. temperaturecooled
  4. additionpoured onto ice
  5. concentrationThe organic layer was concentrated
  6. customthe residue was purified by chromatography on silica gel
  7. washeluting with mixtures of ethyl acetate (0.5% to 1%) in petroleum ether

Sources & evidence

ORD record
ord-bdd6ef69284147598ef139939c7df850
Source dataset
uspto-grants-2014_08
Patent number
US08809397B2

Reaction notes

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