Water → p-Nitrobenzyl 7-{2(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido}-3-chloro-3-cephem-4-carboxylate

HRID 544071Notes

Reaction equation

HRID 544071 reaction equation
S(Cl)([Cl:3])=O.[CH:5]([NH:7][C:8]1[S:9][CH:10]=[C:11]([C:13](=[N:40][O:41][CH3:42])[C:14]([NH:16][CH:17]2[C:38](=[O:39])[N:19]3[C:20]([C:25]([O:27][CH2:28][C:29]4[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][CH:30]=4)=[O:26])=[C:21](O)[CH2:22][S:23][C@H:18]23)=[O:15])[N:12]=1)=[O:6].C(OCC)(=O)C.O>CN(C)C=O>[CH:5]([NH:7][C:8]1[S:9][CH:10]=[C:11]([C:13](=[N:40][O:41][CH3:42])[C:14]([NH:16][CH:17]2[C:38](=[O:39])[N:19]3[C:20]([C:25]([O:27][CH2:28][C:29]4[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][CH:30]=4)=[O:26])=[C:21]([Cl:3])[CH2:22][S:23][C@H:18]23)=[O:15])[N:12]=1)=[O:6]

Participants

6

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 24386Thionyl ChlorideHCID 1317124524-Nitrobenzyl 7-[2-(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido]-3-hydroxy-3-cephem-4-carboxylate

Product 1

HCID 131712431p-Nitrobenzyl 7-{2(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido}-3-chloro-3-cephem-4-carboxylateYield 19.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Thionyl chloride (0.423 g.) was dropwise added to a stirred solution of 4-nitrobenzyl 7-[2-(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido]-3-hydroxy-3-cephem-4-carboxylate (syn isomer, 1 g.) in N,N-dimethylformamide (10 ml.) under ice cooling over 2 minutes, and the solution was stirred at room temperature for 1.1 hours. Ethyl acetate (40 ml.) and water (30 ml.) were added to the resultant solution and shaken sufficiently. The aqueous layer was extracted with ethyl acetate, and the extract was combined with the ethyl acetate layer separated above. The ethyl acetate solution was washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and then concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel (30 g.) and eluted with chloroform and then a mixture of chloroform and ethyl acetate (7:3). The latter eluate was concentrated under reduced pressure to give 4-nitrobenzyl 7-[2-(2-formamido-4-thiazolyl)-2-methoxyiminoacetamido]-3-chloro-3-cephem-4-carboxylate (syn isomer, 0.2 g.), mp 216° C. (dec.).

Workup

  1. stirringshaken sufficiently
  2. extractionThe aqueous layer was extracted with ethyl acetate
  3. customseparated above
  4. washThe ethyl acetate solution was washed with a saturated aqueous solution of sodium chloride
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. washeluted with chloroform
  8. additiona mixture of chloroform and ethyl acetate (7:3)
  9. concentrationThe latter eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-909291a71871401f9c7e7eb8d3e41c0f
Source dataset
uspto-grants-1984_05
Patent number
US04447430

Reaction notes

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