Phosphorus oxychloride → Chloro-N,N-dimethylformiminium chloride

HRID 371242Notes

Reaction equation

HRID 371242 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH:6]1([O:11][N:12]=[C:13]([C:17]2[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=2)[C:14]([OH:16])=O)[CH2:10][CH2:9][CH:8]=[CH:7]1.[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-].[NH2:31][CH:32]1[C:53](=[O:54])[N:34]2[C:35]([C:50]([OH:52])=[O:51])=[C:36]([CH2:39][S:40][C:41]3[CH:46]=[C:45]([C:47]([OH:49])=[O:48])[CH:44]=[CH:43][N:42]=3)[CH2:37][S:38][C@H:33]12.C(=O)(O)[O-].[Na+]>O1CCCC1.CC(C)=O.O>[CH3:25][N+:26]([CH3:29])=[CH:27][Cl:28].[Cl-:3].[CH:6]1([O:11][N:12]=[C:13]([C:17]2[N:18]=[C:19]([NH:22][CH:23]=[O:24])[S:20][CH:21]=2)[C:14]([NH:31][CH:32]2[C:53](=[O:54])[N:34]3[C:35]([C:50]([OH:52])=[O:51])=[C:36]([CH2:39][S:40][C:41]4[CH:46]=[C:45]([C:47]([OH:49])=[O:48])[CH:44]=[CH:43][N:42]=4)[CH2:37][S:38][C@H:33]23)=[O:16])[CH2:10][CH2:9][CH:8]=[CH:7]1

Participants

10

Reactant 5

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 516892Sodium BicarbonateHCID 538228722-(2-Cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetic acidHCID 704870447-Amino-3-(4-carboxypyridin-2-yl)thiomethyl-3-cephem-4-carboxylic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 1317142777-[2-(2-Cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(4-carboxypyridin-2-yl)thiomethyl-3-cephem-4-carboxylic acid

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

The solution of Vilsmeier reagent was prepared from dry N,N-dimethylformamido (0.475 g) and phosphoryl chloride (0.997 g) in dry tetrahydrofuran (1 ml) in a usual manner. A solution of 2-(2-cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer) (1.91 g) in dry tetrahydrofuran (12 ml) was added to the stirred suspension of the solution of Vilsmeier reagent at 0° to 5° C. and the mixture was stirred for 20 minutes. The resulting mixture was added to a solution of 7-amino-3-(4-carboxypyridin-2-yl)thiomethyl-3-cephem-4-carboxylic acid (1.84 g) and sodium bicarbonate (0.84 g) in a mixture of acetone (12 ml) and water (12 ml) at -3° to 0° C. and the mixture was stirred at the same temperature for 40 minutes. The reaction mixture was evaporated under reduced pressure. The residue was adjusted to pH 6.5 with 10% hydrochloric acid, washed with ethyl acetate, concentrated to a small volume and then adjusted to pH 2.9 with 10% hydrochloric acid. The precipitates were collected by filtration, washed with water and dried over phosphorus pentoxide to give 7-[2-(2-cyclopenten-1-yl)oxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(4-carboxypyridin-2-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.74 g).

Workup

  1. stirringthe mixture was stirred at the same temperature for 40 minutes
  2. customThe reaction mixture was evaporated under reduced pressure
  3. washwashed with ethyl acetate
  4. concentrationconcentrated to a small volume
  5. filtrationThe precipitates were collected by filtration
  6. washwashed with water
  7. dry with materialdried over phosphorus pentoxide

Sources & evidence

ORD record
ord-968840a1a7544634b72650258942a56a
Source dataset
uspto-grants-1985_07
Patent number
US04529802

Reaction notes

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