Phosphorus oxychloride → HCID 131712580, compound

HRID 2412747Notes

Reaction equation

HRID 2412747 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH2:6]([O:8][N:9]=[C:10]([C:14]1[N:15]=[C:16]([NH:19][CH:20]=[O:21])[S:17][CH:18]=1)[C:11]([OH:13])=O)[CH3:7].[NH2:22][CH:23]1[C:43](=[O:44])[N:25]2[C:26]([C:40]([OH:42])=[O:41])=[C:27]([CH2:30][S:31][C:32]3[N:36]([CH2:37][CH:38]=[CH2:39])[N:35]=[N:34][N:33]=3)[CH2:28][S:29][C@H:24]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O.CN(C)C=O>[CH3:24][N+:25]([CH3:43])=[CH:26][Cl:3].[Cl-:3].[CH2:6]([O:8][N:9]=[C:10]([C:14]1[N:15]=[C:16]([NH:19][CH:20]=[O:21])[S:17][CH:18]=1)[C:11]([NH:22][CH:23]1[C:43](=[O:44])[N:25]2[C:26]([C:40]([OH:42])=[O:41])=[C:27]([CH2:30][S:31][C:32]3[N:36]([CH2:37][CH:38]=[CH2:39])[N:35]=[N:34][N:33]=3)[CH2:28][S:29][C@H:24]12)=[O:13])[CH3:7]

Participants

9

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 544580772-(2-Formamidothiazol-4-yl)-2-ethoxyiminoacetic acidHCID 704326537-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712580HCID 131712580, compoundYield 173.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

The Vilsmeier reagent was prepared from dry dimethylformamide (0.4 g), phosphorus oxychloride (0.9 g) and dry ethyl acetate (1.6 ml) by the conventional method. Dry ethyl acetate (18 ml) was added thereto and then 2-ethoxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer)(1.3 g) was added thereto at 0° C. The mixture was stirred for 30 minutes at the same temperature. The resulting mixture was added under -10° C. to a stirred solution of 7-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (1.8 g) and trimethylsilylacetamide (4.6 g) in dry ethyl acetate (36 ml), and the mixture was stirred for 1 hour at the same temperature. To the reaction mixture was added water (30 ml). The ethyl acetate layer was separated and extracted with a saturated aqueous solution of sodium bicarbonate (pH 7.5). The aqueous layer was washed three times with ethyl acetate and adjusted to pH 2.0 with conc. hydrochloric acid after addition of ethyl acetate (100 ml). The ethyl acetate layer was separated, washed with a saturated aqueous solution of sodium chloride, dried over magnesium sulfate, treated with an activated charcoal and concentrated to dryness to give 7-[2-ethoxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.56 g).

Workup

  1. customat 0° C
  2. stirringthe mixture was stirred for 1 hour at the same temperature
  3. customThe ethyl acetate layer was separated
  4. extractionextracted with a saturated aqueous solution of sodium bicarbonate (pH 7.5)
  5. washThe aqueous layer was washed three times with ethyl acetate
  6. additionafter addition of ethyl acetate (100 ml)
  7. customThe ethyl acetate layer was separated
  8. washwashed with a saturated aqueous solution of sodium chloride
  9. dry with materialdried over magnesium sulfate
  10. additiontreated with an activated charcoal
  11. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-7961a6f084a6444d9fc40532f3fdadea
Source dataset
uspto-grants-1985_01
Patent number
US04493833

Reaction notes

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