Diisopropyl Ether → HCID 131713192, compound

HRID 905461Notes

Reaction equation

HRID 905461 reaction equation
C[N+](C)=CCl.[Cl-].P(Cl)(Cl)(Cl)=O.[CH:12]([NH:14][C:15]1[S:16][CH:17]=[C:18]([C:20](=[N:24][O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][N:28]=2)[C:21]([OH:23])=O)[N:19]=1)=[O:13].Cl.[NH2:34][CH:35]1[C:60](=[O:61])[N:37]2[C:38]([C:44]([O:46][CH:47]([C:54]3[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=3)[C:48]3[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=3)=[O:45])=[C:39]([CH:42]=[CH2:43])[CH2:40][S:41][C@H:36]12.C[Si](CC(N)=O)(C)C.C(OC(C)C)(C)C>O1CCCC1.C(OCC)(=O)C.O.CN(C)C=O>[CH:12]([NH:14][C:15]1[S:16][CH:17]=[C:18]([C:20](=[N:24][O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][N:28]=2)[C:21]([NH:34][CH:35]2[C:60](=[O:61])[N:37]3[C:38]([C:44]([O:46][CH:47]([C:48]4[CH:49]=[CH:50][CH:51]=[CH:52][CH:53]=4)[C:54]4[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=4)=[O:45])=[C:39]([CH:42]=[CH2:43])[CH2:40][S:41][C@H:36]23)=[O:23])[N:19]=1)=[O:13]

Participants

11

Reactant 6

HCID 7914Diisopropyl EtherHCID 24813Phosphorus oxychlorideHCID 77311Chloro-N,N-dimethylformiminium chlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 12818005Benzhydryl 7-amino-3vinyl-3cephem-4-carboxylate hydrochlorideHCID 53787125HCID 53787125, compound

Product 1

HCID 131713192HCID 131713192, compoundYield 99.6%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

To a suspension of Vilsmeier reagent, which was prepared from N,N-dimethylformamide (1.8 g) and phosphorus oxychloride (3.7 g), in tetrahydrofuran (60 ml) was added 2-(2-formamidothiazol-4-yl)-2-(2-pyridylmethoxyimino)acetic acid (syn isomer) (6.74 g) under ice-cooling with stirring, and the stirring was continued at the same temperature for 30 minutes to prepare the activated acid solution. This solution was added to a solution of benzhydryl 7-amino-3-vinyl-3-cephem-4-carboxylate hydrochloride (8.6 g) and trimethylsilylacetamide (15.7 g) in ethyl acetate (100 ml) at -20° C., and the mixture was stirred at -20° to -5° C. for 2 hours. To the reaction mixture were added ethyl acetate and water, followed by separating the ethyl acetate layer. After the ethyl acetate solution was washed with a saturated aqueous sodium bicarbonate and an aqueous sodium chloride, it was dried over anhydrous magnesium sulfate. Removal of the solvent gave a residue, which was pulverized with diisopropyl ether to obtain benzhydryl 7-[2-(2-formamidothiazol-4-yl)-2-(2-pyridylmethoxyimino)acetamido]-3-vinyl-3-cephem-4-carboxylate (syn isomer) (13.6 g).

Workup

  1. temperaturecooling
  2. customto prepare the activated acid solution
  3. stirringthe mixture was stirred at -20° to -5° C. for 2 hours
  4. customby separating the ethyl acetate layer
  5. washAfter the ethyl acetate solution was washed with a saturated aqueous sodium bicarbonate
  6. dry with materialan aqueous sodium chloride, it was dried over anhydrous magnesium sulfate
  7. customRemoval of the solvent
  8. customgave a residue, which

Sources & evidence

ORD record
ord-386a6e555ec94963bb2b98e3c9227025
Source dataset
uspto-grants-1983_12
Patent number
US04423213

Reaction notes

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