Phosphorus oxychloride → HCID 131712585, compound

HRID 1659748Notes

Reaction equation

HRID 1659748 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:42](=[O:43])[N:24]2[C:25]([C:39]([OH:41])=[O:40])=[C:26]([CH2:29][S:30][C:31]3[N:35]([CH2:36][CH:37]=[CH2:38])[CH:34]=[N:33][N:32]=3)[CH2:27][S:28][C@H:23]12.C(=O)(O)[O-].[Na+]>O.CC(C)=O.C(OCC)(=O)C.CN(C)C=O>[CH3:23][N+:24]([CH3:42])=[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:42](=[O:43])[N:24]2[C:25]([C:39]([OH:41])=[O:40])=[C:26]([CH2:29][S:30][C:31]3[N:35]([CH2:36][CH:37]=[CH2:38])[CH:34]=[N:33][N:32]=3)[CH2:27][S:28][C@H:23]12)=[O:12]

Participants

10

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 27245112-(2-Formylamino-1,3-Thiazol-4-Yl)-2-(Methoxyimino)Acetic AcidHCID 704905787-amino-3-(4-allyl-4H-1,2,4-triazol-3-yl)thiomethyl-3-cephem-4-carboxylic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712585HCID 131712585, compoundYield 56.7%

Reagents, catalysts & solvents 4

HCID 180AcetoneSolventHCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

The Vilsmeier reagent was prepared from dry dimethylformamide (0.44 g), phosphorus oxychloride (0.9 g) and dry ethyl acetate (1.0 ml) by the conventional method. Dry ethyl acetate (20 ml) was added thereto and then 2-methoxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer) (1.1 g) was added thereto at -5° to -10° C. The mixture was stirred for 10 minutes at the same temperature. The resulting mixture was dropwise added at 0° to 5° C. and pH 6.5 to 7.5 with stirring to a solution of 7-amino-3-(4-allyl-4H-1,2,4-triazol-3-yl)thiomethyl-3-cephem-4-carboxylic acid (2.12 g) and sodium bicarbonate (2 g) in a mixture of water (20 ml) and acetone (20 ml), and the mixture was stirred for 20 minutes at the same temperature. The aqueous layer was separated and acetone was evaporated. The aqueous layer was adjusted under ice-cooling and stirring to pH 3.0 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-(4-allyl-4H-1,2,4-triazol-3-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (0.94 g).

Workup

  1. customat -5° to -10° C
  2. additionThe resulting mixture was dropwise added at 0° to 5° C.
  3. stirringthe mixture was stirred for 20 minutes at the same temperature
  4. customThe aqueous layer was separated
  5. customacetone was evaporated
  6. temperaturecooling
  7. stirringstirring to pH 3.0 with 10% hydrochloric acid
  8. customPrecipitates
  9. filtrationwere collected by filtration
  10. washwashed with water
  11. customdried

Sources & evidence

ORD record
ord-4da602b4b4074b05a59795d46b037605
Source dataset
uspto-grants-1981_12
Patent number
US04304770

Reaction notes

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