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

HRID 892492노트

반응식

HRID 892492 반응식
[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

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 124181,1,1,2-Tetrachloroethane용매2회

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온도
60 °C

실험 절차

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 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 (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.

후처리

  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)

출처 및 근거

ORD 기록
ord-e16db3b72f0d4f24af61803fab0781e8
출처 데이터셋
uspto-grants-1992_06
특허 번호
US05118701

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