Phosphorus oxychloride → HCID 131713053, compound

HRID 434994Notes

Reaction equation

HRID 434994 reaction equation
[NH2:1][C:2]1[S:3][CH:4]=[C:5]([C:7](=[N:11][O:12][CH3:13])[C:8]([OH:10])=O)[N:6]=1.P(Cl)(Cl)(Cl)=O.C[Si](CC(N)=O)(C)C.[NH2:27][CH:28]1[C:49](=[O:50])[N:30]2[C:31]([C:46]([OH:48])=[O:47])=[C:32]([O:35][S:36]([C:39]3[CH:45]=[CH:44][C:42]([CH3:43])=[CH:41][CH:40]=3)(=[O:38])=[O:37])[CH2:33][S:34][C@H:29]12.C(=O)(O)[O-].[Na+]>C(OCC)(=O)C.O.CN(C)C=O>[NH2:1][C:2]1[S:3][CH:4]=[C:5]([C:7](=[N:11][O:12][CH3:13])[C:8]([NH:27][CH:28]2[C:49](=[O:50])[N:30]3[C:31]([C:46]([OH:48])=[O:47])=[C:32]([O:35][S:36]([C:39]4[CH:40]=[CH:41][C:42]([CH3:43])=[CH:44][CH:45]=4)(=[O:37])=[O:38])[CH2:33][S:34][C@H:29]23)=[O:10])[N:6]=1

Participants

9

Reactant 5

HCID 24813Phosphorus oxychlorideHCID 1252162-(2-Aminothiazole-4-yl)-2-methoxyiminoacetic acidHCID 357676Acetamide, 2-(trimethylsilyl)-2×HCID 516892Sodium BicarbonateHCID 12775083HCID 12775083, compound

Product 1

HCID 131713053HCID 131713053, compoundYield 66.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

2-(2-Aminothiazol-4-yl)-2-methoxyiminoacetic acid (syn isomer, 0.76 g.), N,N-dimethylformamide (0.33 g.), phosphoryl chloride (1.46 g.), trimethylsilylacetamide (0.5 g.) and ethyl acetate (10 ml.) were treated to give the activated acid solution in a conventional manner. On the other hand, trimethylsilylacetamide (2.7 g.) was added to a suspension of 7-amino-3-tosyloxy-3-cephem-4-carboxylic acid (1.0 g.) in ethyl acetate (15 ml.) and stirred at room temperature. To the solution was added the activated acid solution obtained above at -15° C. all at once, and stirred at -5°-5° C. for an hour. After the resultant solution was chilled to -20° C., water (30 ml.) was added to the chilled solution and adjusted to pH 6.5 with an aqueous solution of sodium bicarbonate. The insoluble substance was removed by filtration. The aqueous layer was separated and adjusted to pH 3.0 with hydrochloric acid. The precipitates were collected by filtration and dried to give 7-[2-(2-aminothiazol-4-yl)-2-methoxyiminoacetamido]-3-tosyloxy-3-cephem-4-carboxylic acid (syn isomer, 1.0 g.).

Workup

  1. customto give the activated acid solution in a conventional manner
  2. additionTo the solution was added the activated acid solution
  3. customobtained above at -15° C. all at once, and
  4. stirringstirred at -5°-5° C. for an hour
  5. customThe insoluble substance was removed by filtration
  6. customThe aqueous layer was separated
  7. filtrationThe precipitates were collected by filtration
  8. customdried

Sources & evidence

ORD record
ord-9bab2195452845f08a22c3a30df7fa92
Source dataset
uspto-grants-1983_08
Patent number
US04399133

Reaction notes

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