Phosphorus oxychloride → HCID 131712018, compound

HRID 1758074Notes

Reaction equation

HRID 1758074 reaction equation
P(Cl)(Cl)(Cl)=O.C[N+](C)=CCl.[Cl-].[O:12]1[C:17]([C:18](=[N:22][O:23][CH2:24][CH:25]=[CH2:26])[C:19]([OH:21])=O)=[CH:16][S:15][CH2:14][CH2:13]1.[NH2:27][CH:28]1[C:38](=[O:39])[N:30]2[C:31]([C:35]([OH:37])=[O:36])=[CH:32][CH2:33][S:34][C@H:29]12.C[Si](CC(N)=O)(C)C.C[Si](C([Si](C)(C)C)C(N)=O)(C)C.C(=O)(O)[O-].[Na+]>C(OCC)(=O)C.O.CN(C)C=O>[O:12]1[C:17]([C:18](=[N:22][O:23][CH2:24][CH:25]=[CH2:26])[C:19]([NH:27][CH:28]2[C:38](=[O:39])[N:30]3[C:31]([C:35]([OH:37])=[O:36])=[CH:32][CH2:33][S:34][C@H:29]23)=[O:21])=[CH:16][S:15][CH2:14][CH2:13]1

Participants

11

Reactant 7

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 516892Sodium BicarbonateHCID 11708267BistrimethylsilylacetamidHCID 12941984(6R)-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidHCID 54460205HCID 54460205, compound

Product 1

HCID 131712018HCID 131712018, compoundYield 81.3%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

N,N-dimethylformamide (0.175 g.), phosphoryl chloride (0.367 g.) and ethyl acetate (0.5 ml.) were treated in a conventional manner to prepare a Vilsmeier reagent and the reagent was added to ethyl acetate (5 ml.). To the solution was added 2-(2,3-dihydro-1,4-oxathiin-6-yl)-2-allyloxyiminoacetic acid (syn isomer, 0.500 g.) at -15° C. and stirred at the same temperature for 20 minutes to give an activated acid solution. The solution was added all at once to a solution of 7-amino-3-cephem-4-carboxylic acid (0.524 g.), trimethylsilylacetamide (1.4 g.) and bis(trimethylsilyl)acetamide (1.5 ml.) in ethyl acetate (7.5 ml.) at -15° C. and stirred at the same temperature for 2 hours. Water (10 ml.) was added to the resultant solution, adjusted to pH 7.0 with an aqueous solution of sodium bicarbonate and the aqueous layer was separated. The aqueous solution was adjusted to pH 3 with 10% hydrochloric acid. The precipitates were collected by filtration and washed with water to give 7-[2-(2,3-dihydro-1,4-oxathiin-6-yl)-2-allyloxyiminoacetamido]-3-cephem-4-carboxylic acid (syn isomer, 0.73 g.).

Workup

  1. customto give an activated acid solution
  2. stirringstirred at the same temperature for 2 hours
  3. customthe aqueous layer was separated
  4. filtrationThe precipitates were collected by filtration
  5. washwashed with water

Sources & evidence

ORD record
ord-c0c44906e16c4f909a316c269031edd6
Source dataset
uspto-grants-1983_02
Patent number
US04371531

Reaction notes

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