N,N-Dimethylaniline → 6-Aminopenicillanic acid

HRID 1414112Notes

Reaction equation

HRID 1414112 reaction equation
[CH3:1][C:2]1([CH3:23])[S:6][C@@H:5]2[C@H:7]([NH:10]C(CC3C=CC=CC=3)=O)[C:8](=[O:9])[N:4]2[C@H:3]1[C:20]([O-:22])=[O:21].[K+].CN(C)C1C=CC=CC=1.C[Si](Cl)(C)C.C(Cl)(Cl)=O>C1C=CC=CC=1.C(Cl)Cl>[CH3:1][C:2]1([CH3:23])[S:6][C@@H:5]2[C@H:7]([NH2:10])[C:8](=[O:9])[N:4]2[C@H:3]1[C:20]([OH:22])=[O:21]

Participants

7

Reactant 4

HCID 949N,N-DimethylanilineHCID 6371PhosgeneHCID 6397ChlorotrimethylsilaneHCID 23664709Penicillin G Potassium

Product 1

HCID 110826-Aminopenicillanic acid

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6344DichloromethaneSolvent

Procedure

To a suspension of 6β-phenylacetamidopenicillanic acid potassium salt (1 mmol.) and N,N-dimethylaniline (3 mmol.) in 6 ml. of dry methylene chloride under nitrogen at 0° there is added 1 mmol. of trimethylsilyl chloride. The mixture is stirred for 30 minutes. Then a solution of 1.26 ml. of 12.5% phosgene in benzene is added to the above trimethylsilyl ester mixture. This reaction mixture is stirred at 0° for 2 hours and then the solvents are removed in vacuo. Fresh dichloromethane (6 ml.) is added followed by 2 mmol. of N,N-dimethylaniline and then 2 mmol. of o-aminothiophenol. The mixture is stirred at 0° for 2 hours and then diluted with aqueous sodium bicarbonate solution and dichloromethane to adjust the pH to 7.5-8.0. The aqueous layer is extracted twice with dichloromethane, cooled in an ice-water bath, and then acidified to pH4. The resulting precipitate is collected, washed with acetone:water (1:1) and then acetone, and finally dried to give the desired product, 6β-aminopenicillanic acid.

Workup

  1. stirringThis reaction mixture is stirred at 0° for 2 hours
  2. customthe solvents are removed in vacuo
  3. additionFresh dichloromethane (6 ml.) is added
  4. stirringThe mixture is stirred at 0° for 2 hours
  5. additiondiluted with aqueous sodium bicarbonate solution and dichloromethane
  6. extractionThe aqueous layer is extracted twice with dichloromethane
  7. temperaturecooled in an ice-water bath
  8. customThe resulting precipitate is collected
  9. washwashed with acetone:water (1:1)
  10. dry with materialacetone, and finally dried

Sources & evidence

ORD record
ord-45b4779ce71a440a96b5bcedc0336950
Source dataset
uspto-grants-1981_02
Patent number
US04252973

Reaction notes

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