Potassium Hydroxide → Bicyclo[2.2.2]oct-5-en-2-one

HRID 2406876Notes

Reaction equation

HRID 2406876 reaction equation
Cl[C:2]1(C#N)[CH2:7][CH:6]2[CH2:8][CH2:9][CH:3]1[CH:4]=[CH:5]2.[OH-:12].[K+]>CS(C)=O.O>[CH:3]12[CH2:9][CH2:8][CH:6]([CH:5]=[CH:4]1)[CH2:7][C:2]2=[O:12]

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 243827Bicyclo[2.2.2]oct-5-ene-2-carbonitrile, 2-chloro-

Product 1

HCID 137507Bicyclo[2.2.2]oct-5-en-2-oneYield 50%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Procedure

To a stirred solution of 5-chloro-5-cyanobicyclo[2,2,2]oct-2-ene (65 g, 0.39 mol) (representing several runs of the foregoing procedure) in dimethyl sulfoxide (500 mL) was added potassium hydroxide (87.4 g, 1.56 mol) and water (30 mL). The resulting mixture was stirred at room temperature for 15 h, diluted with water (1000 mL) and extracted with ether (4×500 mL). The combined ether extracts were washed with brine, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by chromatography on silica gel, eluting with mixtures of diethyl ether (1% to 5%) in petroleum ether, to give bicyclo[2,2,2]oct-5-en-2-one (23.8 g. 50% yield) as a white solid, 1H NMR (300 MHz, CDCl3) δ 1.53˜1.84 (m, 4H), 2.01˜2.02 (m, 2H), 2.96˜2.99 (m, 1H), 3.11˜3.13 (m, 1H), 6.15˜6.21 (m, 1H), 6.43˜6.48 (m, 1H); GCMS (m/z): 122.

Workup

  1. extractionextracted with ether (4×500 mL)
  2. washThe combined ether extracts were washed with brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated
  5. customThe residue was purified by chromatography on silica gel
  6. washeluting with mixtures of diethyl ether (1% to 5%) in petroleum ether

Sources & evidence

ORD record
ord-6a87e0f83f214885977f0782d13bee03
Source dataset
uspto-grants-2014_08
Patent number
US08809397B2

Reaction notes

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