Phosphorus oxychloride → HCID 88737824, compound

HRID 1164564Notes

Reaction equation

HRID 1164564 reaction equation
P(Cl)(Cl)(Cl)=O.C[N+](C)=CCl.[Cl-].[CH:12]([NH:14][C:15]1[S:16][CH:17]=[C:18]([C:20](=[O:24])[C:21]([OH:23])=O)[N:19]=1)=[O:13].[NH2:25][CH:26]1[C:47](=[O:48])[N:28]2[C:29]([C:34]([O:36][CH2:37][C:38]3[CH:43]=[CH:42][C:41]([N+:44]([O-:46])=[O:45])=[CH:40][CH:39]=3)=[O:35])=[C:30]([Cl:33])[CH2:31][S:32][C@H:27]12>O1CCCC1.C[Si](CC(N)=O)(C)C.C(OCC)(=O)C.O.CN(C)C=O>[CH:12]([NH:14][C:15]1[S:16][CH:17]=[C:18]([C:20](=[O:24])[C:21]([NH:25][CH:26]2[C:47](=[O:48])[N:28]3[C:29]([C:34]([O:36][CH2:37][C:38]4[CH:39]=[CH:40][C:41]([N+:44]([O-:46])=[O:45])=[CH:42][CH:43]=4)=[O:35])=[C:30]([Cl:33])[CH2:31][S:32][C@H:27]23)=[O:23])[N:19]=1)=[O:13]

Participants

10

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chloride2×HCID 13116693(2-Formamido-1,3-thiazol-4-yl)(oxo)acetic acidHCID 676435564-Nitrobenzyl 7-amino-3-chloro-3-cephem-4-carboxylate

Product 1

HCID 88737824HCID 88737824, compoundYield 18.1%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×HCID 357676Acetamide, 2-(trimethylsilyl)-Solvent

Procedure

N,N-Dimethylformamide (88 mg) and phosphorus oxychloride (184 mg) were mixed to prepare Vilsmeier reagent in a conventional manner, and the resultant Vilsmeier reagent was suspended in dry tetrahydrofuran (10 ml). To the suspension was added 2-(2-formamidothiazol-4-yl)glyoxylic acid (0.2 g) under ice-cooling with stirring, and the solution was stirred at the same temperature for 30 minutes to prepare the activated acid solution. 4-Nitrobenzyl 7-amino-3-chloro-3-cephem-4-carboxylate (0.4 g) was dissolved in a solution of trimethylsilylacetamide (1.0 g) in ethyl acetate (100 ml). To the solution was added the activated acid solution obtained above all at once at -20° C., and the solution was stirred at -20° to -5° C. for 1.5 hours. After water and ethyl acetate (50 ml) were added to the resultant solution at -20° C., the insoluble substance was separated by filtration, washed with water and acetone in turn and then dried to give 4-nitrobenzyl 7-[2-(2-formamidothiazol-4-yl)glyoxyloylamino]-3-chloro-3-cephem-4-carboxylate (0.1 g).

Workup

  1. temperaturecooling
  2. stirringthe solution was stirred at the same temperature for 30 minutes
  3. customto prepare the activated acid solution
  4. additionTo the solution was added the activated acid solution
  5. customobtained above all at once at -20° C.
  6. stirringthe solution was stirred at -20° to -5° C. for 1.5 hours
  7. customthe insoluble substance was separated by filtration
  8. washwashed with water and acetone in turn
  9. customdried

Sources & evidence

ORD record
ord-fc94575512d240e69937a568cd28589a
Source dataset
uspto-grants-1983_01
Patent number
US04370326

Reaction notes

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