Hydrochloric Acid → HCID 88684178, compound

HRID 1164425Notes

Reaction equation

HRID 1164425 reaction equation
[CH3:1][O:2][N:3]=[C:4]1[C:20](=[O:21])[N:6]2[C:7]([C:12]([O:14][CH2:15][C:16]([Cl:19])([Cl:18])[Cl:17])=[O:13])=[C:8]([CH3:11])[CH2:9][S:10][C@H:5]12.Cl>O1CCCC1.O>[CH3:1][O:2][NH:3][C@@H:4]1[C:20](=[O:21])[N:6]2[C:7]([C:12]([O:14][CH2:15][C:16]([Cl:17])([Cl:18])[Cl:19])=[O:13])=[C:8]([CH3:11])[CH2:9][S:10][C@H:5]12

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 131712938HCID 131712938, compound

Product 1

HCID 88684178HCID 88684178, compoundYield 60.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

In tetrahydrofuran (25 ml) is dissolved 2,2,2-trichloroethyl 7-methoxyimino-3-methyl-3-cephem-4-carboxylate (5.80 g) and under ice-cooling stirring, a 1 M tetrahydrofuran solution of borane-tetrahydrofuran complex (198 ml) is added dropwise over a period of 80 minutes. The reaction mixture is diluted with water (20 ml), adjusted to pH 1 with dilute hydrochloric acid and stirred at room temperature for 1.5 hours. The organic solvent is distilled off, the residual aqueous solution is adjusted to pH 7 with aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The ethyl acetate is then distilled off, the residue is dissolved in a mixture of methanol (120 ml) and 12.5% aqueous ammonium chloride (60 ml) and the mixture is stirred at room temperature for an hour. The organic solvent is distilled off and the residual aqueous solution is extracted with ethyl acetate. The extract is washed with aqueous sodium chloride, dried over magnesium sulfate and concentrated. The oily residue is subjected to silica gel (90 g) column chromatography and elution is carried out with ethyl acetate-methylene chloride. By the above procedure is obtained 2,2,2-trichloroethyl 7β-methoxyamino-3-methyl-3-cephem-4-carboxylate (3.51 g).

Workup

  1. temperatureunder ice-cooling
  2. stirringstirred at room temperature for 1.5 hours
  3. distillationThe organic solvent is distilled off
  4. extractionextracted with ethyl acetate
  5. distillationThe ethyl acetate is then distilled off
  6. dissolutionthe residue is dissolved in a mixture of methanol (120 ml) and 12.5% aqueous ammonium chloride (60 ml)
  7. stirringthe mixture is stirred at room temperature for an hour
  8. distillationThe organic solvent is distilled off
  9. extractionthe residual aqueous solution is extracted with ethyl acetate
  10. washThe extract is washed with aqueous sodium chloride
  11. dry with materialdried over magnesium sulfate
  12. concentrationconcentrated
  13. washThe oily residue is subjected to silica gel (90 g) column chromatography and elution

Sources & evidence

ORD record
ord-4289cc19cc3d4f23a369600f08bdd3ec
Source dataset
uspto-grants-1983_01
Patent number
US04369312

Reaction notes

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