p-Toluenesulfonic acid → p-Nitrobenzyl 7-amino-3-methylenecepham-4-carboxylate p-toluenesulfonate

HRID 443535Notes

Reaction equation

HRID 443535 reaction equation
O(CC([NH:11][CH:12]1[C:33](=[O:34])[N:14]2[CH:15]([C:20]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=3)=[O:21])[C:16](=[CH2:19])[CH2:17][S:18][C@H:13]12)=O)C1C=CC=CC=1.C(Cl)Cl.P(Cl)(Cl)(Cl)(Cl)Cl.[C:44]1([CH3:54])[CH:49]=[CH:48][C:47]([S:50]([OH:53])(=[O:52])=[O:51])=[CH:46][CH:45]=1>CO.N1C=CC=CC=1>[C:44]1([CH3:54])[CH:45]=[CH:46][C:47]([S:50]([OH:53])(=[O:51])=[O:52])=[CH:48][CH:49]=1.[NH2:11][CH:12]1[C:33](=[O:34])[N:14]2[CH:15]([C:20]([O:22][CH2:23][C:24]3[CH:25]=[CH:26][C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=3)=[O:21])[C:16](=[CH2:19])[CH2:17][S:18][C@H:13]12

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 6344DichloromethaneHCID 24819Phosphorus pentachlorideHCID 20837924p-Nitrobenzyl 7-Penoxyacetamido-3-methylenecepham-4-carboxylate

Product 1

HCID 131710312p-Nitrobenzyl 7-amino-3-methylenecepham-4-carboxylate p-toluenesulfonate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1049PyridineSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 965 mg. of p-nitrobenzyl 7-phenoxyacetamido-3-methylenecepham-4-carboxylate in 10 ml. of methylene chloride were added 175 mg. of dry pyridine and 460 mg. of phosphorus pentachloride and the mixture was stirred for five hours at room temperature. Thereafter the reaction mixture was cooled to 0° C. and 50 ml. of cold methanol were added. Following a stirring period of one-hour at room temperature the reaction mixture was evaporated in vacuo to remove the solvents and the residual reaction product mixture was dissolved in a mixture of ethyl acetate and water. The pH was adjusted to pH 7 and the ethyl acetate layer was separated and was washed with water and dried. One equivalent of p-toluene sulfonic acid was added to the dried solution and on cooling 600 mg. of p-nitrobenzyl 7-amino-3-methylenecepham-4-carboxylate p-toluenesulfonate formed as a crystalline precipitate. The product was purified by recrystallization from a mixture of 12 ml. of methanol 24 ml. of ether and 15 ml. of petroleum ether.

Workup

  1. waitFollowing a stirring period of one-hour at room temperature
  2. customthe reaction mixture was evaporated in vacuo
  3. customto remove the solvents
  4. dissolutionthe residual reaction product mixture was dissolved in a mixture of ethyl acetate and water
  5. customthe ethyl acetate layer was separated
  6. washwas washed with water
  7. customdried
  8. temperatureon cooling 600 mg

Sources & evidence

ORD record
ord-f3abb7c364044674ba1e574659a3190c
Source dataset
uspto-grants-1981_04
Patent number
US04260745

Reaction notes

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