Phosphorus oxychloride → HCID 131711621, compound

HRID 2351163Notes

Reaction equation

HRID 2351163 reaction equation
[CH3:1][O:2][N:3]=[C:4]([C:27]1[N:28]=[C:29]([NH:32]C=O)[S:30][CH:31]=1)[C:5]([NH:7][CH:8]1[C:25](=[O:26])[N:10]2[C:11]([C:22]([OH:24])=[O:23])=[C:12]([CH2:15][S:16][C:17]3[S:18][CH:19]=[N:20][N:21]=3)[CH2:13][S:14][C@H:9]12)=[O:6].P(Cl)(Cl)([Cl:37])=O>CO>[ClH:37].[CH3:1][O:2][N:3]=[C:4]([C:27]1[N:28]=[C:29]([NH2:32])[S:30][CH:31]=1)[C:5]([NH:7][CH:8]1[C:25](=[O:26])[N:10]2[C:11]([C:22]([OH:24])=[O:23])=[C:12]([CH2:15][S:16][C:17]3[S:18][CH:19]=[N:20][N:21]=3)[CH2:13][S:14][C@H:9]12)=[O:6]

Participants

4

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 131711622HCID 131711622, compound

Product 1

HCID 131711621HCID 131711621, compoundYield 112.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

7-[2-Methoxyimino-2-(2-formamido-1,3-thiazol-4-yl)acetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (10.8 g.) was added to methanol (200 ml.), and phosphorus oxychloride (7.2 g.) was dropwise added thereto with stirring and ice-cooling at 2° to 9° C. After stirring for 1.5 hours at the same temperature, the reaction mixture was concentrated under reduced pressure on a water bath of 25° to 28° C. to the volume of 100 ml. To the residue was added ether (300 ml.) with stirring and ice-cooling. Precipitates were collected by filtration and dried to give 7-[2-methoxyimino-2-(2-amino-1,3-thiazol-4-yl)acetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid hydrochloride (syn isomer) (12.3 g.). This powder (12.3 g.) was suspended in water (100 ml.) and dissolved by adjusting pH of the suspension to 7.5 by addition of a saturated aqueous solution of sodium bicarbonate. To the solution was added ethyl acetate (100 ml.), and the mixture was adjusted to pH 2.5 with 10% hydrochloric acid. Precipitates were collected by filtration, washed with cold water and dried to give 7-[2-methoxyimino-2-(2-amino-1,3-thiazol-4-yl)acetamido]-3-(1,3,4-thiadiazol-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (6.1 g.). The aqueous layer in the mother liquor was separated and stirred under cooling after addition of sodium chloride. Precipitates were collected by filtration to give the same object compound (3.8 g.). Total yield (9.9 g.). This compound was identified with the compound obtained in the foregoing Examples by I.R. and N.M.R. spectra.

Workup

  1. additionwas dropwise added
  2. temperatureice-cooling at 2° to 9° C
  3. stirringAfter stirring for 1.5 hours at the same temperature
  4. concentrationthe reaction mixture was concentrated under reduced pressure on a water bath of 25° to 28° C. to the volume of 100 ml
  5. additionTo the residue was added ether (300 ml.)
  6. stirringwith stirring
  7. temperatureice-cooling
  8. customPrecipitates
  9. filtrationwere collected by filtration
  10. customdried

Sources & evidence

ORD record
ord-74e9edb3ce8d4ec5b29c6322cdda263b
Source dataset
uspto-grants-1989_10
Patent number
US04871860

Reaction notes

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