N,N-Dimethylaniline → 7-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid

HRID 2412737Notes

Reaction equation

HRID 2412737 reaction equation
CN(C)C1C=CC=CC=1.NC(C(O)=O)CCCC([NH:17][CH:18]1[C:38](=[O:39])[N:20]2[C:21]([C:35]([O-:37])=[O:36])=[C:22]([CH2:25][S:26][C:27]3[N:31]([CH2:32][CH:33]=[CH2:34])[N:30]=[N:29][N:28]=3)[CH2:23][S:24][C@H:19]12)=O.[NH4+].C[Si](Cl)(C)C.P(Cl)(Cl)(Cl)(Cl)Cl.C(OCCO)C>O.C(Cl)Cl>[NH2:17][CH:18]1[C:38](=[O:39])[N:20]2[C:21]([C:35]([OH:37])=[O:36])=[C:22]([CH2:25][S:26][C:27]3[N:31]([CH2:32][CH:33]=[CH2:34])[N:30]=[N:29][N:28]=3)[CH2:23][S:24][C@H:19]12

Participants

8

Reactant 5

HCID 949N,N-DimethylanilineHCID 6397ChlorotrimethylsilaneHCID 8076Glycol monoethyl etherHCID 24819Phosphorus pentachlorideHCID 131712576HCID 131712576, compound

Product 1

HCID 704326537-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acidYield 59.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

N,N-Dimethylaniline (18.2 ml) was added to a mixture of ammonium 7-(5-amino-5-carboxyvaleramido)-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylate (10.0 g), trimethylsilyl chloride (20.9 ml) and methylene chloride (75 ml), and the mixture was stirred under reflux for 2.5 hours. Phosphorus pentachloride (5.83 g) was added thereto at -30° to -35° C. and the mixture was stirred for 2 hours at the same temperature. 2-Ethoxyethanol (38 ml) was added dropwise thereto at the same temperature and the mixture was stirred for 1 hour at the same temperature. Water (80 ml) was added thereto at -5° to -10° C. over 10 minutes and the resulting mixture was stirred for 5 minutes at the same temperature. The aqueous layer was separated and adjusted to pH 4.2 with 28% aqueous solution of ammonia. Precipitates were collected by filtration, washed with 70% aqueous acetone (40 ml) and methanol (40 ml), and dried to give 7-amino-3-(1-allyl-1H-tetrazol-5-yl)thiomethyl-3-cephem-4-carboxylic acid (4.1 g).

Workup

  1. temperatureunder reflux for 2.5 hours
  2. stirringat -30° to -35° C. and the mixture was stirred for 2 hours at the same temperature
  3. stirringat the same temperature and the mixture was stirred for 1 hour at the same temperature
  4. stirringthe resulting mixture was stirred for 5 minutes at the same temperature
  5. customThe aqueous layer was separated
  6. customPrecipitates
  7. filtrationwere collected by filtration
  8. washwashed with 70% aqueous acetone (40 ml) and methanol (40 ml)
  9. customdried

Sources & evidence

ORD record
ord-522f04d62cee416584dabf85dbe939f5
Source dataset
uspto-grants-1985_01
Patent number
US04493833

Reaction notes

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