Hydrochloric Acid → Chloro-N,N-dimethylformiminium chloride

HRID 1982731Notes

Reaction equation

HRID 1982731 reaction equation
P(Cl)(Cl)([Cl:3])=O.[Cl:6][C:7]1[S:11][C:10]([NH:12][CH:13]=[O:14])=[N:9][C:8]=1[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:16]([OH:18])=O.[CH3:29][N+:30]([CH3:33])=[CH:31][Cl:32].[Cl-].C[Si](C)(C)NC(=O)C.[NH2:43][CH:44]1[C:55](=[O:56])[N:46]2[C:47]([C:52]([OH:54])=[O:53])=[C:48]([CH3:51])[CH2:49][S:50][C@H:45]12.C(=O)(O)[O-].[Na+].Cl>C(OCC)(=O)C.O1CCCC1.O.CN(C)C=O>[CH3:29][N+:30]([CH3:33])=[CH:31][Cl:32].[Cl-:3].[Cl:6][C:7]1[S:11][C:10]([NH:12][CH:13]=[O:14])=[N:9][C:8]=1[C:15](=[N:19][O:20][CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[C:16]([NH:43][CH:44]1[C:55](=[O:56])[N:46]2[C:47]([C:52]([OH:54])=[O:53])=[C:48]([CH3:51])[CH2:49][S:50][C@H:45]12)=[O:18]

Participants

13

Reactant 7

HCID 313Hydrochloric AcidHCID 24813Phosphorus oxychlorideHCID 25989Acetamide, N-(trimethylsilyl)-HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 516892Sodium BicarbonateHCID 13475828(6R)-7-amino-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidHCID 540757552-(2-Formamido-5-chlorothiazol-4-yl)-2-tert-butoxycarbonylmethoxyiminoacetic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131714764HCID 131714764, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolvent2×HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent2×

Procedure

Vilsmeier reagent was prepared from phosphorus oxychloride (1.4 g) and dimethyl formamide (0.67 g) in ethyl acetate (2.68 ml) in usual manner. 2-(5-Chloro-2-formamidothiazol-4-yl)-2-t-butoxycarbonylmethoxyiminoacetic acid (syn isomer) (2.8 g) was added to the stirred suspension of Vilsmeier reagent in tetrahydrofuran (30 ml) under ice cooling and stirred for 20 minutes at same temperature to produce an activated solution. N-(trimethylsilyl)acetamide (6.4 g) was added to the stirred suspension of 7-amino-3-methyl-3-cephem-4-carboxylic acid (1.5 g) in tetrahydrofuran (30 ml), and stirred for 20 minutes at 35° C. to 40° C. To the solution was added the above activated solution at -10° C. and stirred at same temperature for 30 minutes. Water and ethyl acetate were 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 sodium bicarbonate. The separated aqueous layer was adjusted to pH 2.0 with 10% aqueous hydrochloric acid and extracted with ethyl acetate. The extract layer was washed with saturated aqueous sodium chloride, dried over magnesium sulfate and evaporated to give 7-[2-(5-chloro-2-formamidothiazol-4-yl)-2-t-butoxycarbonylmethoxyiminoacetamido]-3-methyl-3-cephem-4-carboxylic acid (syn isomer) (3.03 g).

Workup

  1. customto produce an activated solution
  2. stirringstirred for 20 minutes at 35° C. to 40° C
  3. additionTo the solution was added the above activated solution at -10° C.
  4. stirringstirred at same temperature for 30 minutes
  5. extractionextracted with ethyl acetate
  6. washThe extract layer was washed with saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customevaporated

Sources & evidence

ORD record
ord-3e0f32c86dc84ddfa54e0e257c50c30e
Source dataset
uspto-grants-1986_06
Patent number
US04596829

Reaction notes

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