Water → 1-(Tert-butoxycarbonyl)-4-[2,6-difluoro-4-(benzyloxycarbonyl)aminophenyl]piperazine

HRID 266709

반응식

HRID 266709 반응식
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[C:19]([F:20])=[CH:18][C:17]([N+:21]([O-])=O)=[CH:16][C:15]=2[F:24])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([O-])=O.[NH4+].[CH3:29][CH2:30][O:31][C:32](C)=[O:33].O>C1COCC1.CO.[Pd]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[C:19]([F:20])=[CH:18][C:17]([NH:21][C:32]([O:31][CH2:30][C:29]3[CH:18]=[CH:19][CH:14]=[CH:15][CH:16]=3)=[O:33])=[CH:16][C:15]=2[F:24])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

참가 물질

7

반응물 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 2723923Ammonium formateHCID 214626024-(2,6-Difluoro-4-nitro-phenyl)-piperazine-1-carboxylic acid tert-butyl ester

생성물 1

HCID 214626171-(Tert-butoxycarbonyl)-4-[2,6-difluoro-4-(benzyloxycarbonyl)aminophenyl]piperazine수율 67%

시약·촉매·용매 2

HCID 23938Palladium촉매HCID 21899815MeOH tetrahydrofuran용매

실험 절차

The 1-(tert-butoxycarbonyl)-4-(2,6-difluoro-4-nitrophenyl)piperazine (44.7 g, 130 mmol) was dissolved in 20% THF/MeOH (600 mL) in a 2 L flask. Ammonium formate (41 g, 651 mmol) was added portionwise, followed by 10% Pd-C (1.12 g, 2.5 weight %), with cooling in an ice bath. When the addition was completed the ice bath was removed. The flask became slightly warm, and the yellow color disappeared. The reaction mixture was filtered through Celite (washing the filter cake with 500 mL MeOH). The filtrate was concentrated under reduced pressure to give a solid which was then treated with 1 L EtOAc and 500 mL H2O. The layers were separated and then the organic layer was washed again with H2O (500 mL) and once with brine (500 mL). The aqueous portions were back-extracted with more EtOAc (2×300 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated to yield a yellow solid. The crude material was recrystallized from hot EtOAc/hexane to afford 39.11 g (67%) of the title compound as a pale yellow crystalline solid with mp 171°-172° C.

후처리

  1. temperaturewith cooling in an ice bath
  2. additionWhen the addition
  3. customwas removed
  4. temperatureThe flask became slightly warm
  5. filtrationThe reaction mixture was filtered through Celite (
  6. washwashing the filter cake with 500 mL MeOH)
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. customto give a solid which
  9. customThe layers were separated
  10. washthe organic layer was washed again with H2O (500 mL) and once with brine (500 mL)
  11. extractionThe aqueous portions were back-extracted with more EtOAc (2×300 mL)
  12. dry with materialThe combined organic extracts were dried over anhydrous Na2SO4
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customto yield a yellow solid
  16. customThe crude material was recrystallized from hot EtOAc/hexane

출처 및 근거

ORD 기록
ord-16d68f99d1b44a39a01b69459355caff
출처 데이터셋
uspto-grants-1997_07
특허 번호
US05652238

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