Phosphorus oxychloride → HCID 131712604, compound

HRID 2412792Notes

Reaction equation

HRID 2412792 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH3:6][O:7][N:8]=[C:9]([C:13]1[N:14]=[C:15]([NH:18][CH:19]=[O:20])[S:16][CH:17]=1)[C:10]([OH:12])=O.[NH2:21][CH:22]1[C:40](=[O:41])[N:24]2[C:25]([C:37]([OH:39])=[O:38])=[C:26]([CH2:29][S:30][C:31]3[S:35][N:34]=[C:33]([CH3:36])[N:32]=3)[CH2:27][S:28][C@H:23]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.CN(C)C=O>[CH3:23][N+:24]([CH3:40])=[CH:25][Cl:3].[Cl-:3].[CH3:6][O:7][N:8]=[C:9]([C:13]1[N:14]=[C:15]([NH:18][CH:19]=[O:20])[S:16][CH:17]=1)[C:10]([NH:21][CH:22]1[C:40](=[O:41])[N:24]2[C:25]([C:37]([OH:39])=[O:38])=[C:26]([CH2:29][S:30][C:31]3[S:35][N:34]=[C:33]([CH3:36])[N:32]=3)[CH2:27][S:28][C@H:23]12)=[O:12]

Participants

8

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 27245112-(2-Formylamino-1,3-Thiazol-4-Yl)-2-(Methoxyimino)Acetic AcidHCID 15593987HCID 15593987, compound

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712604HCID 131712604, compoundYield 167.7%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

The Vilsmeier reagent was prepared from dry dimethylformamide (0.44 g.), phosphorus oxychloride (0.9 g.) and dry ethyl acetate (1 ml.) by the conventional method. Dry ethyl acetate (15 ml.) was added thereto and then 2-methoxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer) (1.1 g.) was added thereto at 0° C. The mixture was stirred for 30 minutes at the same temperature. The resulting mixture was added at -15° C. to a stirred solution of 7-amino-3-(3-methyl-1,2,4-thiadiazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (1.7 g.) and trimethylsilylacetamide (5.3 g.) in dry ethyl acetate (20 ml.) and the mixture was stirred for 1 hour at the same temperature. The reaction mixture was extracted by adding ethyl acetate (20 ml.) and water (30 ml.). The ethyl acetate layer was separated and extracted with a saturated aqueous solution of sodium bicarbonate (20 ml.). The aqueous layer was adjusted to pH 2.0 with 10% hydrochloric acid. Precipitates were collected by filtration, washed with water and dried to give 7-[2-methoxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(3-methyl-1,2,4-thiadiazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.3 g.).

Workup

  1. customat 0° C
  2. stirringthe mixture was stirred for 1 hour at the same temperature
  3. extractionThe reaction mixture was extracted
  4. additionby adding ethyl acetate (20 ml.) and water (30 ml.)
  5. customThe ethyl acetate layer was separated
  6. extractionextracted with a saturated aqueous solution of sodium bicarbonate (20 ml.)
  7. customPrecipitates
  8. filtrationwere collected by filtration
  9. washwashed with water
  10. customdried

Sources & evidence

ORD record
ord-86f039056f5a4fdba8c2d625bcdabc74
Source dataset
uspto-grants-1985_01
Patent number
US04493833

Reaction notes

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