HCID 826705, compound → 5-Ethylidene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-one

HRID 434702Notes

Reaction equation

HRID 434702 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].[O:6]=[C:7]1[C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2C=C(N2CCN(C)CC2)[C:9]2[CH:25]=[CH:26][CH:27]=[CH:28][C:8]1=2>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.CCOCC.CCCCCC.C1COCC1>[CH:3](=[C:2]1[C:1]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2[CH2:13][C:7](=[O:6])[C:8]2[CH:28]=[CH:27][CH:26]=[CH:25][C:9]1=2)[CH3:4]

Participants

7

Reactant 2

HCID 826705HCID 826705, compoundHCID 178418339Butyllithium

Product 1

HCID 538001305-Ethylidene-5,11-dihydro-10H-dibenzo[a,d]cyclohepten-10-oneYield 98%

Reagents, catalysts & solvents 4

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

To a stirred slurry of ethyltriphenylphosphonium bromide (21 g, 0.057 mole) in ether (400 ml) was added dropwise butyllithium in hexane (48 ml, 1.3 M). To the resulting solution was added a solution of 1-(5-keto-5H-dibenzo[a,d]cyclohepten-10-yl)-4-methylpiperazine (13.5 g, 0.044 mole) in THF (100 ml). The resulting mixture was stirred and heated under reflux for 3.5 hours, cooled and poured into ice H2O (300 ml). The organic phase was separated and the aqueous phase extracted with ether (2×150 ml). The combined organic solutions were concentrated under reduced pressure. The concentrate was stirred with a mixture of 1 N aqueous hydrochloric acid (300 ml) and ether (300 ml). The ether phase was separated, the aqueous phase extracted with ether, and the combined ether solutions dried over Na2SO4, filtered and the filtrate concentrated to 100 ml. Triphenylphosphine oxide was removed by filtration and the filtrate was chromatographed on silica-gel which was eluted with chloroform to yield 10.1 g (98%) of 5-ethylidene-10-oxo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene, m.p. 93°-95° C.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 3.5 hours
  3. temperaturecooled
  4. customThe organic phase was separated
  5. extractionthe aqueous phase extracted with ether (2×150 ml)
  6. concentrationThe combined organic solutions were concentrated under reduced pressure
  7. stirringThe concentrate was stirred with a mixture of 1 N aqueous hydrochloric acid (300 ml) and ether (300 ml)
  8. customThe ether phase was separated
  9. extractionthe aqueous phase extracted with ether
  10. dry with materialthe combined ether solutions dried over Na2SO4
  11. filtrationfiltered
  12. concentrationthe filtrate concentrated to 100 ml
  13. customTriphenylphosphine oxide was removed by filtration
  14. customthe filtrate was chromatographed on silica-gel which
  15. washwas eluted with chloroform

Sources & evidence

ORD record
ord-567c0807ffcb41288b826bf7057e8829
Source dataset
uspto-grants-1983_08
Patent number
US04399141

Reaction notes

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