N,N-Dimethylaniline → 4-Nitrobenzyl 7-amino-3-hydroxy-3-cephem-4-carboxylate

HRID 544008Notes

Reaction equation

HRID 544008 reaction equation
CN(C)C1C=CC=CC=1.C[Si](Cl)(C)C.C1(CC([NH:24][CH:25]2[C:46](=[O:47])[N:27]3[C:28]([C:33]([O:35][CH2:36][C:37]4[CH:42]=[CH:41][C:40]([N+:43]([O-:45])=[O:44])=[CH:39][CH:38]=4)=[O:34])=[C:29]([OH:32])[CH2:30][S:31][C@H:26]23)=O)C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)Cl>C(Cl)Cl.O.CO.C(N(CC)CC)C>[NH2:24][CH:25]1[C:46](=[O:47])[N:27]2[C:28]([C:33]([O:35][CH2:36][C:37]3[CH:38]=[CH:39][C:40]([N+:43]([O-:45])=[O:44])=[CH:41][CH:42]=3)=[O:34])=[C:29]([OH:32])[CH2:30][S:31][C@H:26]12

Participants

9

Reactant 4

HCID 949N,N-DimethylanilineHCID 6397ChlorotrimethylsilaneHCID 24819Phosphorus pentachlorideHCID 67685788(6S)-4-Nitrobenzyl 3-hydroxy-8-oxo-7-(N-phenylacetamido)-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate

Product 1

HCID 681232354-Nitrobenzyl 7-amino-3-hydroxy-3-cephem-4-carboxylateYield 69.5%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

Triethylamine (2.37 g.), dimethylaniline (7.12 g.) and trimethylsilyl chloride (3.93 g.) were added to a stirred suspension of 4-nitrobenzyl 7-(2-phenylacetamido)-3-hydroxy-3-cephem-4-carboxylate (10 g.) in methylene chloride (200 ml.) in turn, and the solution was stirred at room temperature for an hour. Phosphorus pentachloride (4.88 g.) was added to the solution at -30° to -25° C. and stirred at -25° to -20° C. for 3 hours. Methanol (42 ml.) was added to the solution at -25° to -20° C., and stirred for an hour. To the solution was added water (35 ml.) at -25° to -20° C., and the solution was stirred at room temperature. The precipitates were collected by filtration, washed with methylene chloride and diethyl ether in turn, and dried to give 4-nitrobenzyl 7-amino-3-hydroxy-3-cephem-4-carboxylate (5.2 g.), mp 148° C. (dec.).

Workup

  1. stirringstirred at -25° to -20° C. for 3 hours
  2. stirringstirred for an hour
  3. stirringthe solution was stirred at room temperature
  4. filtrationThe precipitates were collected by filtration
  5. washwashed with methylene chloride and diethyl ether in turn
  6. customdried

Sources & evidence

ORD record
ord-f0fac1510c4947ab95efee67966f4e37
Source dataset
uspto-grants-1984_05
Patent number
US04447430

Reaction notes

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