Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 1262759Notes

Reaction equation

HRID 1262759 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](C)(C)NC(=O)C.Cl.[NH2:40][CH:41]1[C:65](=[O:66])[N:43]2[C:44]([C:49]([O:51]C(C3C=CC=CC=3)C3C=CC=CC=3)=[S:50])=[C:45]([CH3:48])[CH2:46][S:47][C@H:42]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:21]=[CH:22][S:23][CH:24]=1)[C:17]([NH:40][CH:41]1[C:65](=[O:66])[N:43]2[C:44]([C:49]([O-:51])=[S:50])=[C:45]([CH3:48])[CH2:46][S:47][C@H:42]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 544727372-t-Butoxycarbonylmethoxyimino-2-(4-thiazolyl)acetic acidHCID 131713528HCID 131713528, compound

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 178429636HCID 178429636, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

Vilsmeier reagent was prepared from phosphorus oxychloride (1.3 g) and dimethylformamide (0.6 g) in ethyl acetate (2.4 ml) in a usual manner. 2-(t-Butoxycarbonylmethoxyimino)-2-(4-thiazolyl)acetic acid (syn isomer) (2.0 g) was added to the stirred suspension of Vilsmeier reagent in ethyl acetate (20 ml) under ice cooling and stirred for 20 minutes at same temperature to produced an activated solution. N-(trimethylsilyl)acetamide (5.8 g) was added to the stirred suspension of benzhydryl 7-amino-3-methylthio-3-cephem-4-carboxylate hydrochloride (2.9 g) in ethyl acetate (30 ml) and stirred for 10 minutes at 40° C. To the solution was added the above activated solution at -10° C. and stirred for 30 minutes at same temperature. Water was added to the reaction mixture and separated organic layer was washed with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride and then dried over magnesium sulfate. The solvent was evaporated to give benzyhydryl 7-[2-(t-butoxycarbonylmethoxyimino)-2-(4-thiazolyl)acetamido]-3-methylthio-3 -cephem-4-carboxylate (syn isomer) (3.62 g).

Workup

  1. customto produced an activated solution
  2. stirringstirred for 10 minutes at 40° C
  3. additionTo the solution was added the above activated solution at -10° C.
  4. stirringstirred for 30 minutes at same temperature
  5. customseparated organic layer
  6. washwas washed with saturated aqueous sodium bicarbonate and saturated aqueous sodium chloride
  7. dry with materialdried over magnesium sulfate
  8. customThe solvent was evaporated

Sources & evidence

ORD record
ord-6a462e2bef704f37bc473d8170cc5c52
Source dataset
uspto-grants-1984_06
Patent number
US04452851

Reaction notes

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