Methyl 11-oxo-6,11-dihydrodibenzo[b,e]oxepine-2-carboxylate → Methyl 11-(3-dimethylaminopropylidene)-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate

HRID 1196996Notes

Reaction equation

HRID 1196996 reaction equation
Br.[Br-].[CH3:3][N:4]([CH3:27])[CH2:5][CH2:6][CH2:7][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.CCCCCC.C([Li])CCC.O=[C:40]1[C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][C:45]=2[CH2:44][O:43][C:42]2[CH:51]=[CH:52][C:53]([C:55]([O:57][CH3:58])=[O:56])=[CH:54][C:41]1=2>O1CCCC1>[CH3:3][N:4]([CH3:27])[CH2:5][CH2:6][CH:7]=[C:40]1[C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][C:45]=2[CH2:44][O:43][C:42]2[CH:51]=[CH:52][C:53]([C:55]([O:57][CH3:58])=[O:56])=[CH:54][C:41]1=2

Participants

5

Reactant 3

HCID 2769045Methyl 11-oxo-6,11-dihydrodibenzo[b,e]oxepine-2-carboxylateHCID 23651404[3-(Dimethylamino)propyl](triphenyl)phosphanium bromide--hydrogen bromide (1/1/1)HCID 178418244HCID 178418244, compound

Product 1

HCID 53998201Methyl 11-(3-dimethylaminopropylidene)-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In this Example, 45 g of (3-dimethylaminopropyl)triphenylphosphonium bromide hydrobromide is suspended in 200 ml of tetrahydrofuran under a nitrogen atmosphere and 82 ml of 1.6N-n-butyl lithium hexane solution is added thereto under ice-cooling. The mixture is stirred under ice-cooling for one hour. To the mixture is dropwise added under ice-cooling a solution obtained by dissolving 10 g of methyl 11-oxo-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate in 200 ml of tetrahydrofuran. After stirring the mixture at room temperature for 2 hours, the mixture is extracted with 800 ml of ethyl acetate. After washing the extract with saturated aqueous sodium chloride solution and drying the extract over anhydrous sodium sulfate, the solvent is distilled away under reduced pressure. The residue is purified by column chromatography on silica gel (eluent: hexane:ethyl acetate:triethylamine=10:10:1) to obtain 2.0 g of trans form and 5.6 g of cis form of the desired product.

Workup

  1. temperatureunder ice-cooling
  2. temperaturecooling for one hour
  3. additionTo the mixture is dropwise added under ice-
  4. temperaturecooling a solution
  5. customobtained
  6. stirringAfter stirring the mixture at room temperature for 2 hours
  7. extractionthe mixture is extracted with 800 ml of ethyl acetate
  8. washAfter washing the
  9. extractionextract with saturated aqueous sodium chloride solution
  10. customdrying the
  11. extractionextract over anhydrous sodium sulfate
  12. distillationthe solvent is distilled away under reduced pressure
  13. customThe residue is purified by column chromatography on silica gel (eluent: hexane:ethyl acetate:triethylamine=10:10:1)

Sources & evidence

ORD record
ord-2b6b36b2a8a74d2f878d9c731a34a6c7
Source dataset
uspto-grants-1992_05
Patent number
US05116863

Reaction notes

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