Formaldehyde → Methyl 11-[2-(4-methylpiperazino)ethylidene]-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate

HRID 5042

Reaktionsgleichung

Reaktionsgleichung von HRID 5042
[CH3:1][N:2]1[CH2:7][CH2:6][NH:5][CH2:4][CH2:3]1.C=O.F[C:11](F)(F)[C:12](O)=O.C=[C:18]1[C:28]2[CH2:27][C:26]3[CH:29]=[CH:30][CH:31]=[CH:32][C:25]=3[CH2:24][O:23][C:22]=2[CH:21]=[CH:20][CH:19]1[C:33]([O:35][CH3:36])=[O:34]>ClCC(Cl)(Cl)Cl>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([CH2:11][CH:12]=[C:27]2[C:26]3[CH:29]=[CH:30][CH:31]=[CH:32][C:25]=3[CH2:24][O:23][C:22]3[CH:21]=[CH:20][C:19]([C:33]([O:35][CH3:36])=[O:34])=[CH:18][C:28]2=3)[CH2:4][CH2:3]1

Komponenten

6

Edukt 4

HCID 712FormaldehydeHCID 6422Trifluoroacetic acidHCID 531671-MethylpiperazineHCID 19797490Methyl 1-methylene-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate

Produkt 1

HCID 53817464Methyl 11-[2-(4-methylpiperazino)ethylidene]-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 124181,1,1,2-TetrachloroethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

1-Methylpiperazine, 30 ml, and 74 g of paraformaldehyde were dissolved in 2 l of tetrachloroethane and 100 ml of trifluoroacetic acid was dropwise added to the solution. After stirring at 60° C. for 2 hours, a solution of 36 g of methyl 1-methylene-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate in 600 ml of tetrachloroethane was dropwise added to the reaction mixture followed by stirring at 90° C. for further 3 hours. The reaction mixture was concentrated to dryness under reduced pressure and 4 N hydrochloric acid aqueous solution was added to the residue to adjust pH to 1. Then, the mixture was washed with diethyl ether. Thereafter, 10 N sodium hydroxide aqueous solution was added to adjust pH to 13. Extraction was performed with 3 l of methylene chloride. After washing with saturated sodium chloride aqueous solution and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The resulting residue was subjected to silica gel column chromatography (eluting solvent; hexane: ethyl acetate: triethylamine=5:5:1) to give 44 g of colorles oily methyl 11-[2-(4-methyl-1-piperazinyl)ethylidene]-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate.

Aufarbeitung

  1. stirringby stirring at 90° C. for further 3 hours
  2. concentrationThe reaction mixture was concentrated to dryness under reduced pressure and 4 N hydrochloric acid aqueous solution
  3. additionwas added to the residue
  4. washThen, the mixture was washed with diethyl ether
  5. additionThereafter, 10 N sodium hydroxide aqueous solution was added
  6. extractionExtraction
  7. washAfter washing with saturated sodium chloride aqueous solution
  8. dry with materialdrying over anhydrous sodium sulfate
  9. distillationthe solvent was distilled off under reduced pressure
  10. washThe resulting residue was subjected to silica gel column chromatography (eluting solvent; hexane: ethyl acetate: triethylamine=5:5:1)

Quellen und Nachweise

ORD-Eintrag
ord-092a67ae3ade42ac8570afefa1b804a7
Quelldatensatz
uspto-grants-1993_09
Patentnummer
US05242931

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