Phosphorus oxychloride → Benzhydryl 7-[4-bromo-2-(2,2,2-trichloroethoxycarbonylmethoxyimino)-3-oxobutyramido]-3-vinyl-3-cephem-4-carboxylate

HRID 569377

Reaktionsgleichung

Reaktionsgleichung von HRID 569377
C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.[Br:12][CH2:13][C:14](=[O:30])[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][CH2:25][C:26]([Cl:29])([Cl:28])[Cl:27])=[O:23])[C:16]([OH:18])=O.Cl.[NH2:32][CH:33]1[C:58](=[O:59])[N:35]2[C:36]([C:42]([O:44][CH:45]([C:52]3[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=3)[C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)=[O:43])=[C:37]([CH:40]=[CH2:41])[CH2:38][S:39][C@H:34]12.C[Si](CC(N)=O)(C)C>O1CCCC1.C(OCC)(=O)C.CN(C)C=O>[Br:12][CH2:13][C:14](=[O:30])[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][CH2:25][C:26]([Cl:29])([Cl:28])[Cl:27])=[O:23])[C:16]([NH:32][CH:33]1[C:58](=[O:59])[N:35]2[C:36]([C:42]([O:44][CH:45]([C:46]3[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=3)[C:52]3[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=3)=[O:43])=[C:37]([CH:40]=[CH2:41])[CH2:38][S:39][C@H:34]12)=[O:18]

Komponenten

9

Edukt 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12818005Benzhydryl 7-amino-3vinyl-3cephem-4-carboxylate hydrochlorideHCID 538664824-Bromo-2-(2,2,2-trichloroethoxycarbonylmethoxyimino)-3-oxobutyric acid

Produkt 1

HCID 131713334Benzhydryl 7-[4-bromo-2-(2,2,2-trichloroethoxycarbonylmethoxyimino)-3-oxobutyramido]-3-vinyl-3-cephem-4-carboxylateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 6228DimethylformamideLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
5 °C

Versuchsvorschrift

Vilsmeier reagent prepared from phosphorus oxychloride (7.1 ml) and N,N-dimethylformamide (6.0 ml) was suspended in dry tetrahydrofuran (25 ml). To this suspension was added 4-bromo-2-(2,2,2-trichloroethoxycarbonylmethoxyimino)-3-oxobutyric acid (25 g), and the mixture was stirred at 5° C. for an hour to prepare the activated acid solution. This solution was added at a time to a solution of benzhydryl 7-amino-3-vinyl-3-cephem-4-carboxylate hydrochloride (16.2 g) and trimethylsilylacetamide (40 g) in ethyl acetate (140 ml) at -30° C., and the mixture was stirred at -15° to -5° C. for an hour. The reaction mixture was extracted with ethyl acetate, and the extract was washed with a saturated aqueous sodium bicarbonate and a saturated aqueous sodium chloride, followed by drying over magnesium sulfate. Removal of the solvent gave benzhydryl 7-[4-bromo-2-(2,2,2-trichloroethoxycarbonylmethoxyimino)-3-oxobutyramido]-3-vinyl-3-cephem-4-carboxylate (26.0 g).

Aufarbeitung

  1. customto prepare the activated acid solution
  2. stirringthe mixture was stirred at -15° to -5° C. for an hour
  3. extractionThe reaction mixture was extracted with ethyl acetate
  4. washthe extract was washed with a saturated aqueous sodium bicarbonate
  5. dry with materialby drying over magnesium sulfate
  6. customRemoval of the solvent

Quellen und Nachweise

ORD-Eintrag
ord-4608693ceca74119b70f4a4e6f2c0be3
Quelldatensatz
uspto-grants-1988_03
Patentnummer
US04731443

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