Hydrochloric Acid → 4-(2-Dimethylaminoethylidene)-1-(2-phenoxyethyl)piperidine dihydrochloride

HRID 962455

반응식

HRID 962455 반응식
C([Li])CCC.[Br-].[CH3:7][N:8]([CH3:30])[CH2:9][CH2:10][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[O:31]([CH2:38][CH2:39][N:40]1[CH2:45][CH2:44][C:43](=O)[CH2:42][CH2:41]1)[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[ClH:47]>C1COCC1.CCOCC>[ClH:47].[ClH:47].[CH3:7][N:8]([CH3:30])[CH2:9][CH:10]=[C:43]1[CH2:44][CH2:45][N:40]([CH2:39][CH2:38][O:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH2:41][CH2:42]1

참가 물질

7

반응물 4

HCID 313Hydrochloric AcidHCID 2724136(2-(Dimethylamino)ethyl)triphenylphosphonium bromideHCID 180020361-(2-Phenoxyethyl)-4-piperidoneHCID 178418339Butyllithium

생성물 1

HCID 190854614-(2-Dimethylaminoethylidene)-1-(2-phenoxyethyl)piperidine dihydrochloride

시약·촉매·용매 2

HCID 3283Diethyl Ether용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

n-Butyllithium (9.13 ml, 2.5M solution in hexanes) was added to a suspension of (2-dimethylaminoethyl)triphenylphosphonium bromide (9.46 g) in dry THF (60 ml) under nitrogen at 0° C. over 5 minutes. The mixture was stirred at 0° C. for 30 minutes and then 1-(2-phenoxyethyl)-4-piperidone (5.0 g) in THF (15 ml) was added dropwise over 5 minutes. The mixture was warmed to ambient temperature and then heated at 60° C. for 5 hours. The mixture was left at ambient temperature for 18 hours and then quenched with water and diluted with ethyl acetate. 2M Hydrochloric acid was added and the mixture was separated. The organic layer was extracted with 2M hydrochloric acid and the combined acidic layers were basified and extracted with dichloromethane to give an oil. The oil was purified by flash column chromatography on silica using dichloromethane and then dichloromethane/methanol (1:1) as the mobile phase. The oil obtained after chromatography was dissolved in ether and treated with ethereal hydrogen chloride. The ether was decanted off and the residual semi-solid was triturated with acetone/ether (1:1) and filtered to give a solid which was recrystallised from IMS to give 4-(2-dimethylaminoethylidene)-1-(2-phenoxyethyl)piperidine dihydrochloride, m.p. 234°-235° C.

후처리

  1. temperatureThe mixture was warmed to ambient temperature
  2. temperatureheated at 60° C. for 5 hours
  3. waitThe mixture was left at ambient temperature for 18 hours
  4. customquenched with water
  5. additiondiluted with ethyl acetate
  6. addition2M Hydrochloric acid was added
  7. customthe mixture was separated
  8. extractionThe organic layer was extracted with 2M hydrochloric acid
  9. extractionextracted with dichloromethane
  10. customto give an oil
  11. customThe oil was purified by flash column chromatography on silica
  12. customThe oil obtained after chromatography
  13. customThe ether was decanted off
  14. customthe residual semi-solid was triturated with acetone/ether (1:1)
  15. filtrationfiltered
  16. customto give a solid which
  17. customwas recrystallised from IMS

출처 및 근거

ORD 기록
ord-488fa014f20040eaa53838fb402a9702
출처 데이터셋
uspto-grants-1998_06
특허 번호
US05760035

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