2-Cyano-6,11-dihydro-11-oxodibenz[b,e]oxepin → 2-Cyano-6,11-dihydro-11-ethylidenedibenz[b,e]oxepin

HRID 894221Notes

Reaction equation

HRID 894221 reaction equation
[C:1]([Li])(C)(C)[CH3:2].[C:6]([C:8]1[CH:23]=[CH:22][C:11]2[O:12][CH2:13][C:14]3[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=3[C:16](=O)[C:10]=2[CH:9]=1)#[N:7]>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.O1CCCC1.CCCCCC>[C:6]([C:8]1[CH:23]=[CH:22][C:11]2[O:12][CH2:13][C:14]3[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=3[C:16](=[CH:1][CH3:2])[C:10]=2[CH:9]=1)#[N:7]

Participants

6

Reactant 2

HCID 124468252-Cyano-6,11-dihydro-11-oxodibenz[b,e]oxepinHCID 178418306HCID 178418306, compound

Product 1

HCID 536734252-Cyano-6,11-dihydro-11-ethylidenedibenz[b,e]oxepin

Reagents, catalysts & solvents 3

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

Suspent 23.6 gm of ethyl triphenylphosphonium bromide in 200 ml of dry tetrahydrofuran add dropwise 2.4 ml of t-butyllithium in hexane with stirring at room temperature under a nitrogen atmosphere. Continue stirring for 3 hours and then cool to -70° C. in a dry ice bath. Add 10 gm. of 2-cyano-6,11-dihydro-11-oxodibenz[b,e]oxepin in 75 ml of dry tetrahydrofuran dropwise over 30 minutes. Continue stirring at -70° C. for 30 minutes, warm to room temperature and continue stirring overnight under a nitrogen atmosphere. Pour the mixture into 400 ml. of ether, filter and wash the filtrate with saturated aqueous sodium chloride solution. Dry over anhydrous magnesium sulfate and strip to dryness. Chromatograph the residue over silica gel, eluting with 5% ethyl acetate in hexane to obtain the final product (5.73 gm).

Workup

  1. stirringContinue stirring for 3 hours
  2. temperaturecool to -70° C. in a dry ice bath
  3. additionAdd 10 gm
  4. stirringContinue stirring at -70° C. for 30 minutes
  5. temperaturewarm to room temperature
  6. stirringcontinue stirring overnight under a nitrogen atmosphere
  7. additionPour the mixture into 400 ml
  8. filtrationof ether, filter
  9. washwash the filtrate with saturated aqueous sodium chloride solution
  10. dry with materialDry over anhydrous magnesium sulfate and strip to dryness
  11. washChromatograph the residue over silica gel, eluting with 5% ethyl acetate in hexane

Sources & evidence

ORD record
ord-080c06b0d92e4e499148774c4771fca7
Source dataset
uspto-grants-1981_08
Patent number
US04282365

Reaction notes

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