Trifluoromethanesulfonic anhydride → 4-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(1-methyl-1H-tetrazol-5-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

HRID 235766

Reaktionsgleichung

Reaktionsgleichung von HRID 235766
C(N(C(C)C)CC)(C)C.O=[C:11]1[CH2:17][C@H:16]2[N:13]([C:14](=[O:35])[C@H:15]2[C:18]([CH3:34])([O:20][C:21]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=2)=[O:22])[CH3:19])[C@H:12]1[C:36]([O:38][CH2:39][C:40]1[CH:45]=[CH:44][C:43]([N+:46]([O-:48])=[O:47])=[CH:42][CH:41]=1)=[O:37].FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[CH3:64][N:65]1[C:69]([SH:70])=[N:68][N:67]=[N:66]1>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH3:19][C:18]([C@@H:15]1[C:14](=[O:35])[N:13]2[C@@H:16]1[CH2:17][C:11]([S:70][C:69]1[N:65]([CH3:64])[N:66]=[N:67][N:68]=1)=[C:12]2[C:36]([O:38][CH2:39][C:40]1[CH:41]=[CH:42][C:43]([N+:46]([O-:48])=[O:47])=[CH:44][CH:45]=1)=[O:37])([O:20][C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][C:28]([N+:31]([O-:33])=[O:32])=[CH:27][CH:26]=1)=[O:22])[CH3:34]

Komponenten

7

Edukt 4

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531Diisopropylethylamine2×HCID 185992114-nitrobenzyl (2R,5R,6R)-3,7-dioxo-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-1-azabicyclo[3.2.0]heptane-2-carboxylateHCID 178482017HCID 178482017, Verbindung

Produkt 1

HCID 867412914-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(1-methyl-1H-tetrazol-5-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylateAusbeute 75,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6344DichloromethaneLösungsmittel5×

Versuchsvorschrift

A solution of N,N-diisopropyl-N-ethylamine (0.0386 ml) in methylene chloride (0.347 ml) was added to a solution of 4-nitrobenzyl (2R,5R,6R)-3,7-dioxo-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-1-azabicyclo[3.2.0]heptane-2-carboxylate (100 mg) and 4-(N,N-dimethylamino)pyridine (2.3 mg) in methylene chloride (5 ml) at -30° C. A solution of trifluoromethanesulfonic anhydride (0.0326 ml) in methylene chloride (0.293 ml) was then added thereto at -30° C. After the mixture was stirred at the same temperature for an hour, a solution of N,N-diisopropyl-N-ethylamine (0.129 ml) in methylene chloride (1.16 ml) and a solution of 1-methyl-1H-tetrazole-5-thiol (42.9 mg) in methylene chloride (2.15 ml) were added successively at -30° C. The mixture was stirred at -30° C. for 30 minutes and allowed to warm to ambient temperature over a period of 30 minutes. After stirring at ambient temperature for 2 hours, the mixture was allowed to stand at 4° C. for 2 days. After removal of the solvent, the residue was dissolved in ethyl acetate. The solution was washed three times with water and an aqueous sodium chloride, dried over magnesium sulfate and then evaporated in vacuo. The residue was chromatographed on deactivated silica gel with 10% water (2 g), eluting with a mixture of benzene and acetone (50:1 to 10:1) to give 4-nitrobenzyl (5R,6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-3-(1-methyl-1H-tetrazol-5-ylthio)-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (89 mg) as an oil.

Aufarbeitung

  1. customat -30° C
  2. stirringThe mixture was stirred at -30° C. for 30 minutes
  3. stirringAfter stirring at ambient temperature for 2 hours
  4. customAfter removal of the solvent
  5. dissolutionthe residue was dissolved in ethyl acetate
  6. washThe solution was washed three times with water
  7. dry with materialan aqueous sodium chloride, dried over magnesium sulfate
  8. customevaporated in vacuo
  9. customThe residue was chromatographed on deactivated silica gel with 10% water (2 g)
  10. washeluting with a mixture of benzene and acetone (50:1 to 10:1)

Quellen und Nachweise

ORD-Eintrag
ord-eae01317edae49ae8c3384caf9766b8b
Quelldatensatz
uspto-grants-1987_02
Patentnummer
US04640915

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