2-Aminothiophenol → 4-nitrobenzyl (5R,6R)-3-(2-aminophenylthio)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate

HRID 235768

Reaktionsgleichung

Reaktionsgleichung von HRID 235768
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].P(Cl)(OC1C=CC=CC=1)(OC1C=CC=CC=1)=O.[NH2:66][C:67]1[CH:72]=[CH:71][CH:70]=[CH:69][C:68]=1[SH:73]>C(#N)C.CN(C1C=CN=CC=1)C>[NH2:66][C:67]1[CH:72]=[CH:71][CH:70]=[CH:69][C:68]=1[S:73][C:11]1[CH2:17][C@H:16]2[N:13]([C:14](=[O:35])[C@H:15]2[C:18]([CH3:19])([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])[CH3:34])[C: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]

Komponenten

7

Edukt 4

HCID 87132-AminothiophenolHCID 75654Diphenyl chlorophosphateHCID 81531Diisopropylethylamine2×HCID 185992114-nitrobenzyl (2R,5R,6R)-3,7-dioxo-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-1-azabicyclo[3.2.0]heptane-2-carboxylate

Produkt 1

HCID 539705804-nitrobenzyl (5R,6R)-3-(2-aminophenylthio)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylateAusbeute 78,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 6342AcetonitrileLösungsmittel4×

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A solution of N,N-diisopropyl-N-ethylamine (0.247 ml) in acetonitrile (2.2 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 (640 mg) and 4-(N,N-dimethylamino)pyridine (14.4 mg) in acetonitrile (32 ml) at 0° C. A solution of diphenyl chlorophosphate (0.257 ml) in acetonitrile (2.3 ml) was then added thereto at 0° C. After the mixture was stirred at 0° C. for 30 minutes, N,N-diisopropyl-N-ethylamine (0.824 ml) and a solution of 2-aminobenzenethiol (155 mg) in acetonitrile (1.4 ml) were added at 0° C. After stirring at 0° C. for an hour, the mixture was evaporated in vacuo and the residue was dissolved in ethyl acetate (50 ml). This solution was washed twice with water (X2) and an aqueous sodium chloride, dried over magnesium sulfate, and then evaporated in vacuo. The residue was chromatographed on silica gel (20 g) eluting with a mixture of benzene and acetone (50:1 to 10:1) to give 4-nitrobenzyl (5R,6R)-3-(2-aminophenylthio)-6-[1-methyl-1-(4-nitrobenzyloxycarbonyloxy)ethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (603 mg) as an oil.

Aufarbeitung

  1. customat 0° C
  2. stirringAfter stirring at 0° C. for an hour
  3. customthe mixture was evaporated in vacuo
  4. dissolutionthe residue was dissolved in ethyl acetate (50 ml)
  5. washThis solution was washed twice with water (X2)
  6. dry with materialan aqueous sodium chloride, dried over magnesium sulfate
  7. customevaporated in vacuo
  8. customThe residue was chromatographed on silica gel (20 g)
  9. washeluting with a mixture of benzene and acetone (50:1 to 10:1)

Quellen und Nachweise

ORD-Eintrag
ord-a9c30c1a07f840e383576b31a683cf9c
Quelldatensatz
uspto-grants-1987_02
Patentnummer
US04640915

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