Phosphorus oxychloride → Benzhydryl 7-(4-bromo-2-methoxyiminoacetoacetamido)-3-vinyl-3-cephem-4-carboxylate

HRID 569342

Reaktionsgleichung

Reaktionsgleichung von HRID 569342
P(Cl)(Cl)(Cl)=O.[Br:6][CH2:7][C:8](=[O:16])[C:9](=[N:13][O:14][CH3:15])[C:10]([OH:12])=O.Cl.[NH2:18][CH:19]1[C:44](=[O:45])[N:21]2[C:22]([C:28]([O:30][CH:31]([C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)[C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[O:29])=[C:23]([CH:26]=[CH2:27])[CH2:24][S:25][C@H:20]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O.CN(C)C=O>[Br:6][CH2:7][C:8](=[O:16])[C:9](=[N:13][O:14][CH3:15])[C:10]([NH:18][CH:19]1[C:44](=[O:45])[N:21]2[C:22]([C:28]([O:30][CH:31]([C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)[C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)=[O:29])=[C:23]([CH:26]=[CH2:27])[CH2:24][S:25][C@H:20]12)=[O:12]

Komponenten

8

Edukt 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12818005Benzhydryl 7-amino-3vinyl-3cephem-4-carboxylate hydrochlorideHCID 536512154-Bromo-2-(methoxyimino)-3-oxobutanoic acid

Produkt 1

HCID 131713160Benzhydryl 7-(4-bromo-2-methoxyiminoacetoacetamido)-3-vinyl-3-cephem-4-carboxylateAusbeute 83,3 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel3×

Versuchsvorschrift

Vilsmeir reagent, which was prepared from N,N-dimethylformamide (0.48 g) and phosphorus oxychloride (1.0 g), was suspended in ethyl acetate (20 ml), and thereto was added 4-bromo-2-methoxyiminoacetoacetic acid (syn isomer) (1.34 g) under ice-cooling, followed by stirring at the same temperature for half an hour to prepare the activated acid solution. This solution was added to a solution of benzhydryl 7-amino-3-vinyl-3-cephem-4-carboxylate hydrochloride (2.15 g) and trimethylsilylacetamide (3.93 g) in ethyl acetate (30 ml) at -20° C., and the mixture was stirred at -20° to 0° C. for 1.5 hours. To the reaction mixture was added ethyl acetate (100 ml) and water (100 ml), and the separated ethyl acetate solution was washed with a saturated aqueous sodium bicarbonate and an aqueous sodium chloride, followed by drying over anhydrous magnesium sulfate. Removal of the solvent gave a residue, which was washed with diethyl ether to obtain benzhydryl 7-(4-bromo-2-methoxyiminoacetoacetamido)-3-vinyl-3-cephem-4 -carboxylate (syn isomer) (2.5 g).

Aufarbeitung

  1. temperaturecooling
  2. customto prepare the activated acid solution
  3. stirringthe mixture was stirred at -20° to 0° C. for 1.5 hours
  4. washthe separated ethyl acetate solution was washed with a saturated aqueous sodium bicarbonate
  5. dry with materialby drying over anhydrous magnesium sulfate
  6. customRemoval of the solvent
  7. customgave a residue, which
  8. washwas washed with diethyl ether

Quellen und Nachweise

ORD-Eintrag
ord-33b25714b53c4cdf8dbeff4da2851222
Quelldatensatz
uspto-grants-1988_03
Patentnummer
US04731443

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