Chloroform → benzhydryl 7-[2-allyloxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetamido]-3-[(Z)-2-(2-pyridyl)vinylthio]-3-cephem-4-carboxylate

HRID 2351137Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2351137
[NH2:1][CH:2]1[C:34](=[O:35])[N:4]2[C:5]([C:18]([O:20][CH:21]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])=[C:6]([S:9]/[CH:10]=[CH:11]\[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=3)[CH2:7][S:8][C@H:3]12.C[Si](NC(N[Si](C)(C)C)=O)(C)C.Cl.[CH2:49]([O:52][N:53]=[C:54]([C:58]1[N:62]=[C:61]([NH2:63])[S:60][N:59]=1)[C:55](Cl)=[O:56])[CH:50]=[CH2:51].C(Cl)(Cl)Cl>C(Cl)Cl.O1CCCC1.C(OCC)(=O)C.C(=O)(O)[O-].[Na+].O>[CH2:49]([O:52][N:53]=[C:54]([C:58]1[N:62]=[C:61]([NH2:63])[S:60][N:59]=1)[C:55]([NH:1][CH:2]1[C:34](=[O:35])[N:4]2[C:5]([C:18]([O:20][CH:21]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)=[O:19])=[C:6]([S:9]/[CH:10]=[CH:11]\[C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][N:13]=3)[CH2:7][S:8][C@H:3]12)=[O:56])[CH:50]=[CH2:51]

Komponenten

10

Edukt 4

HCID 6212ChloroformHCID 875621,3-Bis(trimethylsilyl)ureaHCID 67948085benzhydryl 7-amino-3-[(Z)-2-(2-pyridyl)vinylthio]-3-cephem-4-carboxylateHCID 736584962-Allyloxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetyl chloride hydrochloride

Produkt 1

HCID 131716151benzhydryl 7-[2-allyloxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetamido]-3-[(Z)-2-(2-pyridyl)vinylthio]-3-cephem-4-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittelHCID 516892Sodium BicarbonateLösungsmittel

Versuchsvorschrift

A mixture of benzhydryl 7-amino-3-[(Z)-2-(2-pyridyl) -vinylthio]-3-cephem-4-carboxylate (600 ml) and bis-(trimethylsilyl)urea (981 mg) in methylene chloride (6 ml) was stirred at 30°~35° C. for 30 minutes to give a clear solution. To the clear solution was added 2-allyloxyimino-2-(5-amino-1,2,4-thiadiazol-3yl) acetyl chloride monohydrochloride (syn isomer) (480 mg) at -20° C. and the mixture was stirred for 30 minutes at -10°~-15° C. The mixture was poured into a mixture of chloroform and water. The organic layer was separated and concentrated in vacuo to give a residue. The residue was dissolved in a mixture of tetrahydrofuran, ethyl acetate and dilute aqueous solution of sodium bicarbonate. The organic layer was separated, washed with dilute aqueous solution of sodium bicarbonate and a saturated aqueous solution of sodium chloride in turn, dried over magnesium sulfate and concentrated in vacuo, and the residue was triturated with diisopropyl ether to give benzhydryl 7-[2-allyloxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl) -acetamido]-3-[(Z)-2-(2-pyridyl)vinylthio]-3-cephem-4-carboxylate (syn isomer) (848 mg).

Aufarbeitung

  1. customto give a clear solution
  2. stirringthe mixture was stirred for 30 minutes at -10°~-15° C
  3. customThe organic layer was separated
  4. concentrationconcentrated in vacuo
  5. customto give a residue
  6. customThe organic layer was separated
  7. washwashed with dilute aqueous solution of sodium bicarbonate
  8. dry with materiala saturated aqueous solution of sodium chloride in turn, dried over magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customthe residue was triturated with diisopropyl ether

Quellen und Nachweise

ORD-Eintrag
ord-389852be3e65462f9828cf9c35d6ffc4
Quelldatensatz
uspto-grants-1989_10
Patentnummer
US04871730

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