Phosphorus oxychloride → HCID 131714060, compound

HRID 1154271Notes

Reaction equation

HRID 1154271 reaction equation
P(Cl)(Cl)(Cl)=O.[Cl:6][CH2:7][C:8](=[O:20])[C:9](=[N:13][O:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[C:10]([OH:12])=O.[NH2:21][CH:22]1[C:34](=[O:35])[N:24]2[C:25]([C:31]([OH:33])=[O:32])=[C:26]([CH:29]=[CH2:30])[CH2:27][S:28][C@H:23]12.C[Si](CC(N)=O)(C)C>O1CCCC1.C(OCC)(=O)C.O.CN(C)C=O>[Cl:6][CH2:7][C:8](=[O:20])[C:9](=[N:13][O:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[C:10]([NH:21][CH:22]1[C:34](=[O:35])[N:24]2[C:25]([C:31]([OH:33])=[O:32])=[C:26]([CH:29]=[CH2:30])[CH2:27][S:28][C@H:23]12)=[O:12]

Participants

9

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 128180067-Amino-3vinyl-3-cephem-4-carboxylic acidHCID 248204364-Chloro-2-methoxycarbonylmethoxyimino-3-oxobutyric acid

Product 1

HCID 131714060HCID 131714060, compoundYield 85%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Vilsmeir 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-c4338a9e3aa545d897e269a278bee2b2
Source dataset
uspto-grants-1984_12
Patent number
US04487927

Reaction notes

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