Phosphorus oxychloride → HCID 131712581, compound

HRID 1659744Notes

Reaction equation

HRID 1659744 reaction equation
P(Cl)(Cl)([Cl:3])=O.[CH2:6]([O:9][N:10]=[C:11]([C:15]1[N:16]=[C:17]([NH:20][CH:21]=[O:22])[S:18][CH:19]=1)[C:12]([OH:14])=O)[C:7]#[CH:8].[NH2:23][CH:24]1[C:44](=[O:45])[N:26]2[C:27]([C:41]([OH:43])=[O:42])=[C:28]([CH2:31][S:32][C:33]3[N:37]([CH2:38][CH:39]=[CH2:40])[N:36]=[N:35][N:34]=3)[CH2:29][S:30][C@H:25]12.C[Si](CC(N)=O)(C)C>C(OCC)(=O)C.O.O1CCCC1.CN(C)C=O>[CH3:25][N+:26]([CH3:44])=[CH:27][Cl:3].[Cl-:3].[CH2:6]([O:9][N:10]=[C:11]([C:15]1[N:16]=[C:17]([NH:20][CH:21]=[O:22])[S:18][CH:19]=1)[C:12]([NH:23][CH:24]1[C:44](=[O:45])[N:26]2[C:27]([C:41]([OH:43])=[O:42])=[C:28]([CH2:31][S:32][C:33]3[N:37]([CH2:38][CH:39]=[CH2:40])[N:36]=[N:35][N:34]=3)[CH2:29][S:30][C@H:25]12)=[O:14])[C:7]#[CH:8]

Participants

10

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 537194582-(2-Formamidothiazol-4-yl)-2-(propargyloxyimino)acetic acidHCID 704326537-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

Product 2

HCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 131712581HCID 131712581, compoundYield 144.3%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

The Vilsmeier reagent was prepared from dry dimethylformamide (0.5 g), phosphorus oxychloride (1.3 g) and dry ethyl acetate (2.0 ml) by the conventional method. Dry tetrahydrofuran (20 ml) was added thereto and then 2-(2-propynyl)oxyimino-2-(2-formamidothiazol-4-yl)acetic acid (syn isomer) (1.6 g) was added thereto at 0° C. The mixture was stirred for 30 minutes at the same temperature. The resulting mixture was added at -10° C. to a stirred solution of 7-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (2.0 g) and trimethylsilylacetamide (5.1 g) in dry ethyl acetate (40 ml), and the mixture was stirred for 1 hour at -10° to -20° C. To the reaction mixture was added water (30 ml). The organic layer was separated and extracted with a saturated aqueous solution of sodium bicarbonate (30 ml). The aqueous layer was adjusted to pH 2.2 with conc. hydrochloric acid. Precipitates were collected by filtration, washed with water and dried to give colorless powder of 7-[2-(2-propynyl)oxyimino-2-(2-formamidothiazol-4-yl)acetamido]-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (syn isomer) (2.40 g).

Workup

  1. customat 0° C
  2. stirringthe mixture was stirred for 1 hour at -10° to -20° C
  3. customThe organic layer was separated
  4. extractionextracted with a saturated aqueous solution of sodium bicarbonate (30 ml)
  5. customPrecipitates
  6. filtrationwere collected by filtration
  7. washwashed with water
  8. customdried

Sources & evidence

ORD record
ord-b3a56a1e3d1d43cd89ae6d9cee03dba0
Source dataset
uspto-grants-1981_12
Patent number
US04304770

Reaction notes

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