Phosphorus oxychloride → HCID 131712545, compound

HRID 1155172Notes

Reaction equation

HRID 1155172 reaction equation
P(Cl)(Cl)(Cl)=O.[CH2:6]([O:8][N:9]=[C:10]([C:14]1[N:15]=[C:16]([NH:19][CH:20]=[O:21])[S:17][CH:18]=1)[C:11]([OH:13])=O)[CH3:7].[CH3:22][CH:23]1[CH:28]=[C:27]([C:29]([OH:31])=[O:30])[N:26]2[C:32](=[O:35])[CH:33]([NH2:34])[C@H:25]2[S:24]1.C[Si](CC(N)=O)(C)C>C(=O)=O.CC(C)=O.C(OCC)(=O)C.O.CN(C)C=O>[CH3:22][CH:23]1[CH:28]=[C:27]([C:29]([OH:31])=[O:30])[N:26]2[C:32](=[O:35])[CH:33]([NH:34][C:11](=[O:13])[C:10](=[N:9][O:8][CH2:6][CH3:7])[C:14]3[N:15]=[C:16]([NH:19][CH:20]=[O:21])[S:17][CH:18]=3)[C@H:25]2[S:24]1

Participants

10

Reactant 5

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 128022512-Methyl-7-amino-3-cephem-4-carboxylic acidHCID 544580772-(2-Formamidothiazol-4-yl)-2-ethoxyiminoacetic acidHCID 178474914HCID 178474914, compound

Product 1

HCID 131712545HCID 131712545, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent4×HCID 18522661Acetone cardiceSolvent

Procedure

To dimethylformamide (0.65 g) was added dried ethyl acetate (3 ml), and the mixture was solidified by dropwise addition of phosphorus oxychloride (1.37 g) under cooling at 0° C. in dry ice-acetone bath over 15 minutes followed by stirring at the same temperature for a while. Dried ethyl acetate (20 ml) was added thereto and 2-ethoxyimino-2-(2-formylaminothiazol-4-yl)acetic acid (syn isomer), which can be represented as 2-ethoxyimino-2-(2-formylimino-2,3-dihydrothiazol-4-yl)acetic acid (syn isomer), (2.00 g) was added thereto. The resulting mixture was stirred for an hour at the same temperature and thereto was added ethyl acetate (30 ml) and stirring was continued at the same temperature for an hour, during which period a homogeneous solution was obtained. Thus obtained solution was added dropwise over 15 minutes at -15° C. to a solution, which was prepared by stirring a mixture of 2-methyl-7-amino-3-cephem-4-carboxylic acid (1.60 g) and trimethylsilylacetamide (6.86 g) in ethyl acetate (100 ml) for an hour at room temperature. The mixture was stirred for an hour at the same temperature and thereto was added water (30 ml) and then the temperature of the mixture was permitted to rise to room temperature. The precipitates were collected by filtration washed with water and then dried over phosphorus pentoxide under reduced pressure to give 2-methyl-7-[2-ethoxyimino-2-(2-formylaminothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid (syn isomer), which can be represented as 2-methyl-7-[2-ethoxyimino-2-(2-formylimino-2,3-dihydrothiazol-4-yl)acetamido]-3-cephem-4-carboxylic acid (syn isomer), (1.68 g). The ethyl acetate layer in the mother liquor was separated, washed with water, dried over magnesium sulfate and then concentrated under reduced pressure to give powder of the same compound (1.54 g). Total yield: 3.22 g.

Workup

  1. additionwas added
  2. stirringThe resulting mixture was stirred for an hour at the same temperature
  3. stirringstirring
  4. waitwas continued at the same temperature for an hour, during which period
  5. customa homogeneous solution was obtained
  6. additionThus obtained solution was added dropwise over 15 minutes at -15° C. to a solution, which
  7. customwas prepared
  8. stirringby stirring
  9. stirringThe mixture was stirred for an hour at the same temperature
  10. customto rise to room temperature
  11. filtrationThe precipitates were collected by filtration
  12. washwashed with water
  13. dry with materialdried over phosphorus pentoxide under reduced pressure

Sources & evidence

ORD record
ord-8417a586dc7e463bba4ee08b591bfd31
Source dataset
uspto-grants-1981_11
Patent number
US04299829

Reaction notes

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