Phosphorus oxychloride → HCID 131714060, compound

HRID 569446

Reaction equation

HRID 569446 reaction equation
C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.[Cl:12][CH2:13][C:14](=[O:26])[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])[C:16]([OH:18])=O.[NH2:27][CH:28]1[C:40](=[O:41])[N:30]2[C:31]([C:37]([OH:39])=[O:38])=[C:32]([CH:35]=[CH2:36])[CH2:33][S:34][C@H:29]12.C[Si](CC(N)=O)(C)C>O1CCCC1.C(OCC)(=O)C.O.CN(C)C=O>[Cl:12][CH2:13][C:14](=[O:26])[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])[C:16]([NH:27][CH:28]1[C:40](=[O:41])[N:30]2[C:31]([C:37]([OH:39])=[O:38])=[C:32]([CH:35]=[CH2:36])[CH2:33][S:34][C@H:29]12)=[O:18]

Participants

10

Reactant 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 128180067-Amino-3vinyl-3-cephem-4-carboxylic acidHCID 248204364-Chloro-2-[(2-methoxy-2-oxoethoxy)imino]-3-oxobutanoic acid

Product 1

HCID 131714060HCID 131714060, compoundYield 85%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Vilsmeier reagent prepared from N,N-dimethylformamide (3.76 ml) and phosphorus oxychloride (4.46 ml) was suspended in dry tetrahydrofuran (50 ml). To the suspension was added 4-chloro-2-methoxycarbonylmethoxyimino-3-oxobutyric acid (syn isomer) (10.5 g), and the mixture was stirred under ice-cooling to prepare the activated acid solution. This solution was added at a time to a solution of 7-amino-3-vinyl-3-cephem-4-carboxylic acid (10 g) and trimethylsilylacetamide (35 g) in ethyl acetate (110 ml) at -30° C. After the reaction mixture was stirred at -15° C. for an hour, the resultant solution was poured into water (100 ml) and then extracted with ethyl acetate (200 ml). The extract was washed with a saturated aqueous sodium chloride and dried over magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was triturated with diisopropyl ether to give 7-(4-chloro-2-methoxycarbonylmethoxyimino-3-oxobutyramido)-3-vinyl-3-cephem-4-carboxylic acid (syn isomer) (16.75 g).

Workup

  1. temperaturecooling
  2. customto prepare the activated acid solution
  3. stirringAfter the reaction mixture was stirred at -15° C. for an hour
  4. extractionextracted with ethyl acetate (200 ml)
  5. washThe extract was washed with a saturated aqueous sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent was evaporated under reduced pressure
  8. customthe residue was triturated with diisopropyl ether

Sources & evidence

ORD record
ord-4fddd52f64f94f689b9b6d6a9e648490
Source dataset
uspto-grants-1988_03
Patent number
US04731443

Linked notes

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