홈MCP워크벤치Skills
홈워크벤치알림마이페이지
llms.txt · MCP 가이드개인정보처리방침 · 이용약관 · 지원v1.8.0
  1. 홈
  2. /반응

Piperazine → 1-{[3-(Dimethylamino)phenoxy]phenyl}piperazine

HRID 47254
노트
인쇄 미리보기

반응식

HRID 47254 반응식
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-])=O.[CH3:11][N:12]([CH3:20])[C:13]1[CH:14]=[C:15]([OH:19])[CH:16]=[CH:17][CH:18]=1.[OH-].[K+].[NH:23]1[CH2:28][CH2:27]N[CH2:25][CH2:24]1.C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O.C(=O)([O-])[O-].[K+].[K+].FC(F)(F)C(O)=O>CN(C)C=O.O1CCCC1.O.C(OCC)(=O)C>[CH3:11][N:12]([CH3:20])[C:13]1[CH:14]=[C:15]([CH:16]=[CH:17][CH:18]=1)[O:19][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]1[CH2:27][CH2:28][NH:23][CH2:24][CH2:25]1
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

12

반응물 7

HCID 4837PiperazineHCID 6422Trifluoroacetic acidHCID 69451-Chloro-2-nitrobenzeneHCID 74213-(Dimethylamino)phenolHCID 11430Potassium CarbonateHCID 14797Potassium HydroxideHCID 90495Di-tert-butyl dicarbonate

생성물 1

HCID 218649061-{[3-(Dimethylamino)phenoxy]phenyl}piperazine

시약·촉매·용매 4

HCID 962Water용매2회HCID 6228Dimethylformamide용매HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매

실험 절차

1-Chloro-2-nitrobenzene (15.0 g), 3-(dimethylamino)phenol (13.0 g) and potassium hydroxide (11.8 g) was dissolved in N,N-dimethylformamide (350 mL) and boiled under reflux for 18 hrs. The reaction was then cooled, and poured into water, and worked up by standard procedure using ethyl acetate. The crude product was purified by silicagel chromatography (heptane:ethyl acetate:triethylamine/80:10:10). The pure intermediate was dissolved in a mixture of ethanol (200 mL) and acetic acid (20 mL). After addition of Pd/C (5%, 4.5 g), the reaction mixture was shaken under hydrogen atmosphere (3 bar) for 3 hrs. The reaction mixture was filtered and after neutralisation worked up by standard procedure using ethyl acetate affording pure aniline (11.2 g). The crude aniline, bis-(2-chloroethyl)amine hydrochloride (8.6 g) and chlorobenzene (200 mL) was boiled under reflux for 48 hrs. The reaction mixture was cooled to room temperature, and the volatile solvents evaporated in vacuo to give the crude 1-{[3-(dimethylamino)phenoxy]phenyl}piperazine (18.6 g). A solution of the crude piperazine, di-tert-butyl dicarbonate (32 g) and potassium carbonate (68 g) in tetrahydrofuran:water/1:1, was heated at 50° C. for 18 hrs. The organic layer was separated and the water phase extracted with ethyl acetate. The collected organic phases were worked up by standard procedure followed by purification by silicagel chromatography (heptane:ethyl acetate/8:2) affording pure BOC-protected 1-{[3-dimethyl)phenoxy]phenyl}piperazine (9.4 g). A solution of the BOC-derivative in a mixture of dry THF (30 mL) and trifluoroacetic acid (30 mL) was stirred at room temperature for 1 h. The volatile solvents were evaporated in vacuo and ethyl acetate and 1 N aqueous sodium hydroxide were added. The organic phase was collected and worked up by standard procedure giving pure 1-{[3-(dimethylamino)phenoxy]phenyl}piperazine (6.0 g). A mixture of a part of the pure piperazine (1.37 g), 3-(2-bromoethyl)-1H-indole (1.0 g), potassium carbonate (2.2 g), potassium iodide (cat.) and methyl isobutyl ketone was boiled under reflux for 24 hrs. The mixture was cooled to room temperature, filtered, and the volatile solvents evaporated in vacuo to give an oil which was purified by silicagel chromatography (heptane:ethyl acetate:triethylamine/26:70:4) to give the title compound as an oil. The title compound was crystallised as its oxalate from acetone (1.27 g). Mp 210-203° C.

후처리

  1. temperatureunder reflux for 18 hrs
  2. temperatureThe reaction was then cooled
  3. customThe crude product was purified by silicagel chromatography (heptane:ethyl acetate:triethylamine/80:10:10)
  4. dissolutionThe pure intermediate was dissolved in a mixture of ethanol (200 mL) and acetic acid (20 mL)
  5. additionAfter addition of Pd/C (5%, 4.5 g)
  6. filtrationThe reaction mixture was filtered
  7. temperatureunder reflux for 48 hrs
  8. customthe volatile solvents evaporated in vacuo
  9. customto give the crude 1-{[3-(dimethylamino)phenoxy]phenyl}piperazine (18.6 g)
  10. customThe organic layer was separated
  11. extractionthe water phase extracted with ethyl acetate
  12. customfollowed by purification by silicagel chromatography (heptane:ethyl acetate/8:2)
  13. customaffording pure BOC-
  14. stirringwas stirred at room temperature for 1 h
  15. customThe volatile solvents were evaporated in vacuo and ethyl acetate and 1 N aqueous sodium hydroxide
  16. additionwere added
  17. customThe organic phase was collected

출처 및 근거

ORD 기록
ord-b19cb8f2ce7746cc990b0dca6d55bf47
출처 데이터셋
uspto-grants-2004_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06699864B2

반응 노트

불러오는 중…

이 페이지에서참가 물질실험 절차후처리출처 및 근거반응 노트