Phosphorus pentachloride → 4-Nitrobenzyl 7-[2-ethoxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetamido]-3-cephem-4-carboxylate

HRID 2287003Notes

Reaction equation

HRID 2287003 reaction equation
P(Cl)(Cl)(Cl)(Cl)Cl.[CH2:7]([O:9][N:10]=[C:11]([C:15]1[N:19]=[C:18]([NH2:20])[S:17][N:16]=1)[C:12]([OH:14])=O)[CH3:8].[NH2:21][CH:22]1[C:42](=[O:43])[N:24]2[C:25]([C:29]([O:31][CH2:32][C:33]3[CH:38]=[CH:37][C:36]([N+:39]([O-:41])=[O:40])=[CH:35][CH:34]=3)=[O:30])=[CH:26][CH2:27][S:28][C@H:23]12.C[Si](CC(N)=O)(C)C.C(=O)(O)[O-].[Na+]>C(Cl)Cl>[CH2:7]([O:9][N:10]=[C:11]([C:15]1[N:19]=[C:18]([NH2:20])[S:17][N:16]=1)[C:12]([NH:21][CH:22]1[C:42](=[O:43])[N:24]2[C:25]([C:29]([O:31][CH2:32][C:33]3[CH:34]=[CH:35][C:36]([N+:39]([O-:41])=[O:40])=[CH:37][CH:38]=3)=[O:30])=[CH:26][CH2:27][S:28][C@H:23]12)=[O:14])[CH3:8]

Participants

7

Reactant 5

HCID 24819Phosphorus pentachlorideHCID 357676Acetamide, 2-(trimethylsilyl)-HCID 516892Sodium BicarbonateHCID 12775080p-Nitrobenzyl 7-amino-3-cephem-4-carboxylateHCID 543509922-Ethoxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetic acid

Product 1

HCID 1317122414-Nitrobenzyl 7-[2-ethoxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetamido]-3-cephem-4-carboxylateYield 103.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

To a cold solution of phosphorus pentachloride (2.5 g) in methylene chloride (60 ml) was added 2-ethoxyimino-2-(5-amino-1,2,4-thiadiazol-3-yl)acetic acid (syn isomer) (2.16 g) at -15° C. and the mixture was stirred for 30 minutes at the same temperature. On the other hand, a mixture of 4-nitrobenzyl 7-amino-3-cephem-4-carboxylate (4.0 g) and trimethylsilylacetamide (12 g) in methylene chloride (60 ml) was warmed to make a clear solution and then cooled to -10° C. The solution was added to the above activated mixture and the mixture was stirred for 0.5 hour at 0° to 5° C. The reaction mixture was poured into cold aqueous solution (150 ml) of sodium bicarbonate (7.0 g). The organic layer was dried over magnesium sulfate and evaporated to dryness. The residue was pulverized with diethyl ether and precipitates were collected by filtration and dried to give 4-nitrobenzyl 7-[2-ethoxyimino-2 -(5-amino-1,2,4-thiadiazol-3-yl)acetamido]-3-cephem-4-carboxylate (syn isomer) (5.5 g), mp. 120° to 125° C. (dec.).

Workup

  1. temperaturewas warmed
  2. additionThe solution was added to the above activated mixture
  3. stirringthe mixture was stirred for 0.5 hour at 0° to 5° C
  4. dry with materialThe organic layer was dried over magnesium sulfate
  5. customevaporated to dryness
  6. customprecipitates
  7. filtrationwere collected by filtration
  8. customdried

Sources & evidence

ORD record
ord-c6839c1949e242878b5159e5079d275f
Source dataset
uspto-grants-1981_05
Patent number
US04268509

Reaction notes

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