Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 1650919Notes

Reaction equation

HRID 1650919 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH3:6][N+:7]([CH3:10])=[CH:8][Cl:9].[Cl-].C[Si](CC(N)=O)(C)C.[CH3:20][C:21]([O:23][CH2:24][C:25]1[CH2:34][S:33][C@@H:28]2[C@H:29](N)[C:30](=[O:31])[N:27]2[C:26]=1[C:35]([OH:37])=[O:36])=[O:22]>C(OCC)(=O)C.O1CCCC1.O.CN(C)C=O>[CH3:6][N+:7]([CH3:10])=[CH:8][Cl:9].[Cl-:3].[CH3:20][C:21]([O:23][CH2:24][C:25]1[CH2:34][S:33][C@@H:28]2[CH2:29][C:30](=[O:31])[N:27]2[C:26]=1[C:35]([OH:37])=[O:36])=[O:22]

Participants

10

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 4413287-Aminocephalosporanic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 12302722Cephalosporanic Acid

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent2×

Procedure

Vilsmeier reagent was prepared from phosphorus oxychloride (1.1 g) and N,N-dimethylformamide (0.5 g) in ethyl acetate (2.0 ml) in a conventional manner. 2-[2-(2,2,2-Trifluoroacetamido)-5-chlorothiazol-4-yl]-2-propargloxyiminoacetic acid (syn isomer, 2.2 g) was added to the stirred suspension of Vilsmeier reagent in tetrahydrofuran (22 ml) under ice cooling and stirred for 20 minutes at same temperature [Solution A]. Trimethylsilylacetamide (5.1 g) was added to the stirred suspension of 7-aminocephalosporanic acid (1.5 g) in tetrahydrofuran (30 ml); and the mixture was stirred for 30 minutes at 35° to 40° C. To the solution was added the solution [Solution A] at -10° C., and the resulting solution was stirred at the same temperature for 30 minutes. Water and ethyl acetate were added to the reaction mixture at -10° C. The organic layer was separated and added to water. The mixture was adjusted to pH 7.5 with a saturated aqueous solution of sodium bicarbonate. The aqueous layer was separated and adjusted to pH 2.0 with 10% hydrochloric acid, and then extracted with ethyl acetate. The extract was washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate and evaporated under reduced pressure to give 7-[2-(2,2,2-trifluoroacetamido)-5-chlorothiazol-4-yl]-2-propargyloxyiminoacetamido]cephalosporanic acid (syn isomer, 2.51 g).

Workup

  1. stirringthe resulting solution was stirred at the same temperature for 30 minutes
  2. customThe organic layer was separated
  3. additionadded to water
  4. customThe aqueous layer was separated
  5. extractionextracted with ethyl acetate
  6. washThe extract was washed with a saturated aqueous solution of sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-a6501dcb13674885b5618edd0cddc47c
Source dataset
uspto-grants-1990_05
Patent number
US04925948

Reaction notes

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