Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 358083Notes

Reaction equation

HRID 358083 reaction equation
P(Cl)(Cl)([Cl:3])=O.[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:24]=[CH:23][S:22][N:21]=1)[C:17]([OH:19])=O)=[O:12])([CH3:9])([CH3:8])[CH3:7].[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-].C[Si](C)(C)NC(=O)C.[NH2:39][CH:40]1[C:50](=[O:51])[N:42]2[C:43]([C:47]([OH:49])=[O:48])=[CH:44][CH2:45][S:46][C@H:41]12>C(OCC)(=O)C.O.CN(C)C=O>[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-:3].[C:6]([O:10][C:11]([CH2:13][O:14][N:15]=[C:16]([C:20]1[N:24]=[CH:23][S:22][N:21]=1)[C:17]([NH:39][CH:40]1[C:50](=[O:51])[N:42]2[C:43]([C:47]([OH:49])=[O:48])=[CH:44][CH2:45][S:46][C@H:41]12)=[O:19])=[O:12])([CH3:7])([CH3:8])[CH3:9]

Participants

10

Reactant 5

HCID 24813Phosphorus oxychlorideHCID 25989Acetamide, N-(trimethylsilyl)-HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 12941984(6R)-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidHCID 539872492-Tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1317136317-[2-Tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetamido]-3-cephem-4-carboxylic acid

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

Vilsmeier reagent was prepared from N,N-dimethylformamide (0.31 g) and phosphorus oxychloride (0.64 g) in a usual manner. 2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3-yl)acetic acid (syn isomer) (1.0 g) was added to a stirred suspension of the Vilsmeier reagent prepared above in ethyl acetate (11 ml) under ice-cooling, and the stirring was continued for 30 minutes at the same temperature to produce an activated acid solution. N-Trimethylsilylacetamide (3.2 g) was added to a stirred suspension of 7-amino-3-cephem-4-carboxylic acid (0.7 g) in ethyl acetate (20 ml), and the stirring was continued at 40° to 43° C. for 30 minutes. To this solution was added the above activated acid solution at -10° C., followed by stirring at the same temperature for 30 minutes. Water (10 ml) was added to the resultant solution, and the separated organic layer was washed with water, dried over magnesium sulfate and then evaporated to give 7-[2-tert-butoxycarbonylmethoxyimino-2-(1,2,4-thiadiazol-3 -yl)acetamido]-3-cephem-4-carboxylic acid (syn isomer) (1.4 g).

Workup

  1. temperaturecooling
  2. customto produce an activated acid solution
  3. waitthe stirring was continued at 40° to 43° C. for 30 minutes
  4. additionTo this solution was added the above activated acid solution at -10° C.
  5. washthe separated organic layer was washed with water
  6. dry with materialdried over magnesium sulfate
  7. customevaporated

Sources & evidence

ORD record
ord-374aa297e6b34d99a18ab498272327aa
Source dataset
uspto-grants-1984_08
Patent number
US04464369

Reaction notes

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