Trifluoromethanesulfonic anhydride → HCID 56609997, Verbindung

HRID 235775Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 235775
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.[N:64]1[N:65]=[N:66][N:67]2[C:72]=1[CH:71]=[CH:70][C:69]([SH:73])=[N:68]2>ClCCl.CN(C1C=CN=CC=1)C.CN(C)C=O>[CH3:34][C:18]([C@@H:15]1[C:14](=[O:35])[N:13]2[C@@H:16]1[CH2:17][C:11]([S:73][C:69]1[CH:70]=[CH:71][C:72]3[N:67]([N:66]=[N:65][N:64]=3)[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:26]=[CH:27][C:28]([N+:31]([O-:33])=[O:32])=[CH:29][CH:30]=1)=[O:22])[CH3:19]

Komponenten

8

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 1785277156-Mercaptotetrazolo[4,5-b]pyridazine

Produkt 1

HCID 56609997HCID 56609997, VerbindungAusbeute 71,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6228DimethylformamideLösungsmittelHCID 6344DichloromethaneLösungsmittel3×

Reaktionsbedingungen

Temperatur
20 °C

Versuchsvorschrift

A solution of N,N-diisopropyl-N-ethylamine (0.231 ml) in dichloromethane (2.08 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 (600 mg) and 4-(N,N-dimethylamino)pyridine (13.5 mg) in dichloromethane (30.0 ml) at -30° C. To this mixture was added a solution of trifluoromethanesulfonic anhydride (0.196 ml) in dichloromethane (3.72 ml) and stirring was continued at -30° C. for 20 minutes. N,N-Diisopropyl-N-ethylamine (0.680 ml) and a solution of tetrazolo[1,5-b]pyridazine-6-thiol (0.256 g) in N,N-dimethylformamide (2.30 ml) were added to the mixture at -30° C. The resultant mixture was allowed to warm to 20° C. over a period of 2 hours, and then evaporated in vacuo. The residue was dissolved in ethyl acetate (100 ml), washed in turn with cold water (x3) and an aqueaus sodium chloride, dried over magnesium sulfate and evaporated in vacuo. The residue was chromatographed on deactivated silica gel with 15% water (7.5 g), eluting with a mixture of benzene and acetone (20:1 to 6:1). The fractions containing the desired compound were collected and diluted with benzene to result in precipitation of crystals, which, after cooling in a refrigerator, were collected by filtration to give 4-nitrobenzyl (5R, 6R)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-7-oxo-3-(tetrazolo[1,5-b]pyridazin-6-ylthio)-1azabicyclo[3.2.0]hept-2-ene-2-carboxylate (0.533 g). Crystallization of the mother liquor from ethyl acetate and n-hexane gave the same product (0.0663 g) as a pale yellow powder.

Aufarbeitung

  1. customevaporated in vacuo
  2. dissolutionThe residue was dissolved in ethyl acetate (100 ml)
  3. washwashed in turn with cold water (x3)
  4. dry with materialan aqueaus sodium chloride, dried over magnesium sulfate
  5. customevaporated in vacuo
  6. customThe residue was chromatographed on deactivated silica gel with 15% water (7.5 g)
  7. washeluting with a mixture of benzene and acetone (20:1 to 6:1)
  8. additionThe fractions containing the desired compound
  9. customwere collected
  10. additiondiluted with benzene
  11. customto result in precipitation of crystals, which
  12. temperatureafter cooling in a refrigerator
  13. filtrationwere collected by filtration

Quellen und Nachweise

ORD-Eintrag
ord-804c68b2a9404c098e61c6613935bd35
Quelldatensatz
uspto-grants-1987_02
Patentnummer
US04640915

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