Sodium Bicarbonate → 2-Methyl-7-[2-methoxyimino-2-(2-formylaminothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid

HRID 261857Notes

Reaction equation

HRID 261857 reaction equation
[CH3:1][CH:2]1[CH:7]=[C:6]([C:8]([OH:10])=[O:9])[N:5]2[C:11](=[O:26])[CH:12]([NH:13][C:14](=[O:25])[C:15]([C:17]3[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=3)=O)[C@H:4]2[S:3]1.C(=O)(O)[O-].[Na+].O.O.O.C([O-])(=O)C.[Na+].Cl.[CH3:41][O:42][NH2:43]>O.C(OCC)(=O)C>[CH3:1][CH:2]1[CH:7]=[C:6]([C:8]([OH:10])=[O:9])[N:5]2[C:11](=[O:26])[CH:12]([NH:13][C:14](=[O:25])[C:15](=[N:43][O:42][CH3:41])[C:17]3[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=3)[C@H:4]2[S:3]1

Participants

8

Reactant 5

HCID 516892Sodium Bicarbonate2×HCID 521874O-Methylhydroxylamine hydrochlorideHCID 23665404Sodium Acetate TrihydrateHCID 1317114932-Methyl-7-[2-(2-formylaminothiazol-4-yl)glyoxylamido]-3-cephem-4-carboxylic acidHCID 178427249HCID 178427249, compound

Product 1

HCID 1317114952-Methyl-7-[2-methoxyimino-2-(2-formylaminothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 2-methyl-7-[2-(2-formylaminothiazol-4-yl)glyoxylamido]-3-cephem-4-carboxylic acid, which can be represented as 2-methyl-7-[2-(2-formylimino-2,3-dihydrothiazol-4-yl)glyoxylamido]-3-cephem-4-carboxylic acid, (792 mg.) in water (20 ml.) was added sodium bicarbonate (168 mg.) with stirring. To thus obtained solution were added sodium acetate trihydrate (272.2 mg.) and O-methylhydroxylamine hydrochloride (334 mg.), and the mixture was stirred for 2 hours at 48° to 50° C. After cooling the reaction mixture, a saturated aqueous sodium bicarbonate solution (10 ml.) and ethyl acetate (15 ml.) were added thereto in order to dissolve the precipitated insoluble material. The aqueous layer was separated, washed with ethyl acetate, adjusted to pH 1 with 2N hydrochloric acid and then extracted with ethyl acetate. The ethyl acetate extract was washed with a saturated aqueous sodium chloride solution, dried over magnesium sulfate and then concentrated. The residue was pulverized in diethyl ether, collected by filtration and then dried to give 2-methyl-7-[2-methoxyimino-2-(2-formylaminothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid (syn isomer), which can be represented as 2-methyl-7-[2-methoxyimino-2-(2-formylimino-2,3-dihydrothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid (syn isomer), (505 mg.). This compound was recrystallized from methanol to give white crystals of the pure object compound.

Workup

  1. stirringthe mixture was stirred for 2 hours at 48° to 50° C
  2. temperatureAfter cooling the reaction mixture
  3. dissolutionin order to dissolve the precipitated insoluble material
  4. customThe aqueous layer was separated
  5. washwashed with ethyl acetate
  6. extractionextracted with ethyl acetate
  7. extractionThe ethyl acetate extract
  8. washwas washed with a saturated aqueous sodium chloride solution
  9. dry with materialdried over magnesium sulfate
  10. concentrationconcentrated
  11. filtrationcollected by filtration
  12. customdried

Sources & evidence

ORD record
ord-5203050edba043c89596f4d677f2a3b0
Source dataset
uspto-grants-1979_05
Patent number
US04152433

Reaction notes

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