Phosphorus oxychloride → HCID 131712231, compound

HRID 1075243Notes

Reaction equation

HRID 1075243 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8](=[N:12][O:13][CH3:14])[C:9]([OH:11])=O)[N:3]=1.P(Cl)(Cl)(Cl)=O.[NH2:20][CH:21]1[C:41](=[O:42])[N:23]2[C:24]([C:28]([O:30][CH2:31][C:32]3[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=3)=[O:29])=[CH:25][CH2:26][S:27][C@H:22]12.C[Si](CC(N)=O)(C)C>C(Cl)Cl.CN(C)C=O>[NH2:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C:8](=[N:12][O:13][CH3:14])[C:9]([NH:20][CH:21]2[C:41](=[O:42])[N:23]3[C:24]([C:28]([O:30][CH2:31][C:32]4[CH:33]=[CH:34][C:35]([N+:38]([O-:40])=[O:39])=[CH:36][CH:37]=4)=[O:29])=[CH:25][CH2:26][S:27][C@H:22]23)=[O:11])[N:3]=1

Participants

7

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12775080p-Nitrobenzyl 7-amino-3-cephem-4-carboxylateHCID 54097963HCID 54097963, compound

Product 1

HCID 131712231HCID 131712231, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
3 °C

Procedure

A mixture of 2-(4-aminopyrimidin-2-yl)-2-methoxyiminoacetic acid (syn isomer) (2.32 g) and phosphoryl chloride (4.6 g) in methylene chloride (15 ml) was stirred for 30 minutes at 3° C. To the mixture was added dropwise a solution of N,N-dimethylformamide (3.0 ml) in methylene chloride (15 ml) and stirred for 40 minutes at 3° C. A solution of 4-nitrobenzyl 7-amino-3-cephem-4-carboxylate (3.02 g) and trimethylsilyl acetamide (15 g) in methylene chloride (60 ml) was cooled to -5° C. and added to the activated acid solution obtained above. The mixture was stirred for 30 minutes at 3° to 5° C. and for additional 30 minutes at ambient temperature. The solvent was evaporated to dryness and the residue was dissolved in ethyl acetate (200 ml). The solution was washed with an aqueous solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was washed with diethyl ether to give 4-nitrobenzyl 7-[2-(4-aminopyrimidin-2-yl)-2-methoxyiminoacetamido]-3-cephem-4-carboxylate (syn isomer) (3.1 g) as a powder, mp 125°-131° C. (dec.).

Workup

  1. stirringstirred for 40 minutes at 3° C
  2. additionadded to the activated acid solution
  3. customobtained above
  4. stirringThe mixture was stirred for 30 minutes at 3° to 5° C. and for additional 30 minutes at ambient temperature
  5. customThe solvent was evaporated to dryness
  6. dissolutionthe residue was dissolved in ethyl acetate (200 ml)
  7. washThe solution was washed with an aqueous solution of sodium bicarbonate and water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customevaporated to dryness
  10. washThe residue was washed with diethyl ether

Sources & evidence

ORD record
ord-e228bc0276ef4b19b20f2d319acc2747
Source dataset
uspto-grants-1983_07
Patent number
US04395411

Reaction notes

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