Fluorenone → 2-(9H-Fluoren-9-ylidene)acetonitrile

HRID 2190294Notes

Reaction equation

HRID 2190294 reaction equation
[H-].[Na+].[C:3]([CH2:5]P(=O)(OCC)OCC)#[N:4].[CH:14]1[C:26]2[C:25](=O)[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:18]=2[CH:17]=[CH:16][CH:15]=1.[Cl-].[NH4+]>COCCOC.C(OCC)(=O)C>[CH:14]1[C:26]2[C:25](=[CH:5][C:3]#[N:4])[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:18]=2[CH:17]=[CH:16][CH:15]=1

Participants

7

Reactant 4

HCID 10241FluorenoneHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 75676Diethyl (cyanomethyl)phosphonate

Product 1

HCID 6090532-(9H-Fluoren-9-ylidene)acetonitrile

Reagents, catalysts & solvents 2

HCID 80711,2-DimethoxyethaneSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

528 mg of NaH (in a 55-65% suspension in oil; 13.2 mmol, 2.2 eq) in suspension in 20 mL of DME were introduced into a 100 mL Woulff bottle equipped with a straight condenser. 1.94 mL of diethyl cyanomethylphosphonate (12 mmol, 2 eq) in solution in 5 mL of DME were then added dropwise. After the release of gas, the reaction medium was heated under reflux for 15 min, then 1.08 g of fluoren-9-one (6 mmol, 1 eq) in solution in 5 mL of DME were added dropwise. After refluxing for 2 hours, the reaction was stopped by addition of 40 mL of an aqueous ammonium chloride solution. The medium was taken up with ethyl acetate, and the aqueous phase was extracted with ethyl acetate. The organic phases were collected, dried over MgSO4, filtered and concentrated. The fluoren-9-ylidene-acetonitrile was purified by chromatography over silica gel (CH2Cl2/heptane elution gradient: 80/20).

Workup

  1. customequipped with a straight condenser
  2. temperatureAfter the release of gas, the reaction medium was heated
  3. temperatureunder reflux for 15 min
  4. temperatureAfter refluxing for 2 hours
  5. extractionthe aqueous phase was extracted with ethyl acetate
  6. customThe organic phases were collected
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe fluoren-9-ylidene-acetonitrile was purified by chromatography over silica gel (CH2Cl2/heptane elution gradient: 80/20)

Sources & evidence

ORD record
ord-d3a2aad49f0a4e3dbd8b3a7bf1f74e05
Source dataset
uspto-grants-2012_12
Patent number
US08324396B2

Reaction notes

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