p-Nitrobenzyl 7-[2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylate → 7-[2-Tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylic acid

HRID 358087Notes

Reaction equation

HRID 358087 reaction equation
[C:1]([O:5][C:6]([CH2:8][O:9][N:10]=[C:11]([C:38]1[N:42]=[CH:41][S:40][N:39]=1)[C:12]([NH:14][CH:15]1[C:36](=[O:37])[N:17]2[C:18]([C:23]([O:25]CC3C=CC([N+]([O-])=O)=CC=3)=[O:24])=[C:19]([Cl:22])[CH2:20][S:21][C@H:16]12)=[O:13])=[O:7])([CH3:4])([CH3:3])[CH3:2]>CO.O1CCCC1.C(O)(=O)C.[Pd]>[C:1]([O:5][C:6]([CH2:8][O:9][N:10]=[C:11]([C:38]1[N:42]=[CH:41][S:40][N:39]=1)[C:12]([NH:14][CH:15]1[C:36](=[O:37])[N:17]2[C:18]([C:23]([OH:25])=[O:24])=[C:19]([Cl:22])[CH2:20][S:21][C@H:16]12)=[O:13])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 1

HCID 131713632p-Nitrobenzyl 7-[2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylate

Product 1

HCID 1317136357-[2-Tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylic acidYield 36.2%

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

p-Nitrobenzyl 7-[2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylate (syn isomer) (4.9 g) dissolved in a mixed solvent of methanol (30 ml), tetrahydrofuran (30 ml) and acetic acid (1 ml). After adding 10% palladium on carbon (2.5 g) thereto, the mixture was subjected to catalytic reduction at ambient temperature under atmospheric pressure. The catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure. To the residue were added water and ethyl acetate, and the mixture was adjusted to pH 7.5 with 20% aqueous sodium carbonate. The separated aqueous layer was adjusted to pH 2.0 with 10% hydrochloric acid and then extracted with ethyl acetate. The extract was washed with a saturated aqueous sodium chloride and dried over magnesium sulfate. The solvent was removed by evaporation to give 7-[2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-chloro-3-cephem-4-carboxylic acid (syn isomer) (1.4 g).

Workup

  1. customwas subjected to catalytic reduction at ambient temperature under atmospheric pressure
  2. customThe catalyst was removed by filtration
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. additionTo the residue were added water and ethyl acetate
  5. extractionextracted with ethyl acetate
  6. washThe extract was washed with a saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customThe solvent was removed by evaporation

Sources & evidence

ORD record
ord-b42d90f910b844f9879ecfc322c5fb1f
Source dataset
uspto-grants-1984_08
Patent number
US04464369

Reaction notes

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