Hydrochloric Acid → Chloro-N,N-dimethylformiminium chloride

HRID 1906079Notes

Reaction equation

HRID 1906079 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:21]=[CH:22][S:23][CH:24]=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](CC(N)=O)(C)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(=O)([O-])[O-].[K+].[K+].Cl>C(OCC)(=O)C.O1CCCC1.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:21]=[CH:22][S:23][CH:24]=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

13

Reactant 7

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12941984(6R)-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidHCID 544727372-t-Butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1317142047-[2-t-Butoxycarbonylmethoxyimino2-(4-thiazolyl)acetamido]-3-cephem-4-carboxylic acid

Reagents, catalysts & solvents 4

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

Vilsmeier reagent was prepared from phosphorus oxychloride (0.76 g) and N,N-dimethylformamide (0.36 g) in ethyl acetate (1.44 ml) in a usual manner. 2-t-Butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetic acid (sny isomer) (1.2 g) was added to the stirred suspension of Vilsmeier reagent in ethyl acetate (20 ml) under ice-cooling and the mixture was stirred for 20 minutes at the same temperature to prepare an activated acid solution. Trimethylsilylacetamide (3.5 g) was added to the stirred suspension of 7-amino-3-cephem-4-carboxylic acid (0.76 g) in tetrahydrofuran (15 ml) and the mixture was stirred for 20 minutes at 35° to 40° C. To the solution was added the above activated acid solution at -10° C. and the mixture was stirred for 30 minutes at the same temperature. Water was added to the reaction mixture and the separated organic layer was added to water and the mixture was adjusted to pH 7.5 with saturated aqueous solution of potassium carbonate. The separated aqueous layer was adjusted to pH 2.0 with 10% hydrochloric acid and extracted with ethyl acetate. The extracted layer was washed with saturated aqueous slution of sodium chloride, dried over magnesium sulfate and evaporated to give 7-[2-t-butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetamido]-3-cephem-4-carboxylic acid (syn isomer) (1.4 g).

Workup

  1. temperaturecooling
  2. customto prepare an activated acid solution
  3. stirringthe mixture was stirred for 20 minutes at 35° to 40° C
  4. additionTo the solution was added the above activated acid solution at -10° C.
  5. stirringthe mixture was stirred for 30 minutes at the same temperature
  6. extractionextracted with ethyl acetate
  7. washThe extracted layer was washed with saturated aqueous slution of sodium chloride
  8. dry with materialdried over magnesium sulfate
  9. customevaporated

Sources & evidence

ORD record
ord-86fcf7cce2e846529fe2b0dccbbd49bf
Source dataset
uspto-grants-1987_03
Patent number
US04649136

Reaction notes

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