Sodium Chloride → (3R,5R,6R)-6-amino-3-(3-amino-2-oxoimidazolidin-1-yl)-3-(p-nitrobenzyloxycarbonyl)-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane

HRID 1463438노트

반응식

HRID 1463438 반응식
[NH2:1][C@@H:2]1[C:8](=[O:9])[N:7]2[C@@H:3]1[S:4][C@@:5]([N:23]1[CH2:27][CH2:26][N:25]([N:28]=CC3C=CC=CC=3)[C:24]1=[O:36])([C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=1)=[O:11])[CH2:6]2.[N+](C1C=C([N+]([O-])=O)C=CC=1NN)([O-])=O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)([O-])O.[Na+].[Cl-].[Na+]>O.CO.C(Cl)Cl>[NH2:1][C@@H:2]1[C:8](=[O:9])[N:7]2[C@@H:3]1[S:4][C@@:5]([N:23]1[CH2:27][CH2:26][N:25]([NH2:28])[C:24]1=[O:36])([C:10]([O:12][CH2:13][C:14]1[CH:15]=[CH:16][C:17]([N+:20]([O-:22])=[O:21])=[CH:18][CH:19]=1)=[O:11])[CH2:6]2

참가 물질

9

반응물 5

HCID 5234Sodium ChlorideHCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 3772977(2,4-Dinitrophenyl)hydrazineHCID 54330068(3R,5R,6R)-6-amino-3-(3-benzylideneamino-2-oxo-imidazolidin-1-yl)-3-(p-nitrobenzyloxycarbonyl)-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane

생성물 1

HCID 53724867(3R,5R,6R)-6-amino-3-(3-amino-2-oxoimidazolidin-1-yl)-3-(p-nitrobenzyloxycarbonyl)-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane수율 81.8%

시약·촉매·용매 3

HCID 887Methanol용매HCID 962Water용매HCID 6344Dichloromethane용매

실험 절차

In a mixed solvent consisting of 200 ml of methylene chloride and 70 ml of methanol was dissolved 13.2 g of (3R,5R,6R)-6-amino-3-(3-benzylideneamino-2-oxoimidazolidin-1-yl)-3-(p-nitrobenzyloxycarbonyl)-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane. Thereto were added 10.3 g of 2,4-dinitrophenylhydrazine and 9.83 g of p-toluenesulfonic acid monohydrate in this order. The mixture was stirred at room temperature for 1.5 hours. The insolubles were removed by filtration. The insolubles were washed with a mixed solvent consisting of 60 ml of methylene chloride and 20 ml of methanol. The washings and the filtrate obtained previously were combined, and mixed with 50 ml of water. The aqueous layer was separated. The organic layer was mixed with 30 ml of water and adjusted to pH 1.2 with 6N hydrochloric acid. The aqueous layer was separated. This aqueous layer and the aqueous layer obtained previously were combined and adjusted to pH 7 with sodium hydrogencarbonate. Thereto was added sodium chloride to saturation. Then, the aqueous layer was extracted with 150 ml of methylene chloride. The aqueous layer was further extracted 7 times each with 50 ml of methylene chloride. The extracts were combined with the organic layer obtained previously, and dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (eluant: chloroform/methanol=50/1 to 15/1) to obtain 8.93 g (yield: 81.8%) of (3R, 5R,6R)-6-amino-3-(3-amino-2-oxoimidazolidin-1-yl)-3-(p-nitrobenzyloxycarbonyl)-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane.

후처리

  1. customThe insolubles were removed by filtration
  2. washThe insolubles were washed with a mixed solvent
  3. customThe washings and the filtrate obtained previously
  4. customThe aqueous layer was separated
  5. additionThe organic layer was mixed with 30 ml of water
  6. customThe aqueous layer was separated
  7. customThis aqueous layer and the aqueous layer obtained previously
  8. extractionThen, the aqueous layer was extracted with 150 ml of methylene chloride
  9. extractionThe aqueous layer was further extracted 7 times each with 50 ml of methylene chloride
  10. customobtained previously
  11. dry with materialdried over anhydrous magnesium sulfate
  12. customThe solvent was removed by distillation under reduced pressure
  13. customThe residue was purified by column chromatography (eluant: chloroform/methanol=50/1 to 15/1)

출처 및 근거

ORD 기록
ord-4d3ac436a57f454991f42e5a79f21a8a
출처 데이터셋
uspto-grants-1994_04
특허 번호
US05300497

반응 노트

불러오는 중…