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

HRID 981963Notes

Reaction equation

HRID 981963 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][NH:5][CH2:4][CH2:3]1.C=O.F[C:11](F)(F)C(O)=O.[CH2:17]=[C:18]1[C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=2[CH2:22][O:21][C:20]2[CH:29]=[CH:30][C:31]([C:33]([O:35][CH3:36])=[O:34])=[CH:32][C:19]1=2>ClCC(Cl)(Cl)Cl>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([CH2:11][CH:17]=[C:18]2[C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][C:23]=3[CH2:22][O:21][C:20]3[CH:29]=[CH:30][C:31]([C:33]([O:35][CH3:36])=[O:34])=[CH:32][C:19]2=3)[CH2:4][CH2:3]1

Participants

6

Reactant 4

HCID 712FormaldehydeHCID 6422Trifluoroacetic acidHCID 531671-MethylpiperazineHCID 10106958HCID 10106958, compound

Product 1

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

Reagents, catalysts & solvents 1

HCID 124181,1,1,2-TetrachloroethaneSolvent2×

Conditions

Temperature
60 °C

Procedure

4-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 11-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 (eluent; hexane:ethyl acetate:triethylamine=5:5:1) to give 44 g of methyl 11-[2-(4-methyl-1-piperazinyl)ethylidene]-6,11-dihydrodibenz[b,e]oxepin-2-carboxylate as colorless oil.

Workup

  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

Sources & evidence

ORD record
ord-716478c38b5445bea164fc3e24e1da0d
Source dataset
uspto-grants-1991_02
Patent number
US04994463

Reaction notes

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