Ammonia → 6-Aminopenicillanic acid

HRID 1834097Notes

Reaction equation

HRID 1834097 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.Cl[Si](Cl)(C)C.P(Cl)(Cl)(Cl)(Cl)Cl.C(N)(=S)C.ClC(Cl)(Cl)SCl.N.O.N>ClCCl.O.CO>[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

12

Reactant 8

HCID 222AmmoniaHCID 949N,N-DimethylanilineHCID 6398DichlorodimethylsilaneHCID 11666Trichloromethanesulfenyl chlorideHCID 24819Phosphorus pentachlorideHCID 2723949ThioacetamideHCID 12896473Azane;hydrateHCID 23664709Penicillin G Potassium

Product 1

HCID 110826-Aminopenicillanic acid

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

In dichloromethane (25 volume parts) was suspended potassium salt of benzylpenicillin (6.0 parts) and to the suspension, under stirring at room temperature, N,N-dimethylaniline (5.2 volume parts) and dichlorodimethylsilane (1.6 volume parts) were added in succession and, the mixture was stirred for 30 minutes. Then, the mixture was chilled to -30° C and phosphorus pentachloride (3.6 parts) was added, followed by stirring for 2 hours at -30° C. Then, to the resultant thioacetamide (1.5 parts) was added and the mixture was further stirred at -40 to -25° C for 1.5 hours. Then, under stirring at -40° C, to the mixture methanol (20 volume parts) was added drop by drop in such a manner that the temperature of -30° C was not exceeded, followed by the addition of trichloromethanesulfenyl chloride (2.3 volume parts). The mixture was stirred for 30 minutes. Under stirring at -30° C to the mixture water (5 volume parts) was added and, then, to the mixture concentrated aqueous ammonia (20 volume parts) was slowly added dropwise. Then, on an icewater bath, the resultant was adjusted to pH 4.1 with ammonia water, followed by stirring for 1 hour. The resultant precipitate was recovered by filtration, washed with 50% methanol and dichloromethane and dried. The procedure yielded 6-aminopenicillanic acid (2.2 part). In IR spectrum, this product was found in good agreement with an authentic sample.

Workup

  1. stirringthe mixture was stirred for 30 minutes
  2. temperatureThen, the mixture was chilled to -30° C
  3. stirringby stirring for 2 hours at -30° C
  4. stirringthe mixture was further stirred at -40 to -25° C for 1.5 hours
  5. additionwas added drop by drop in such a manner that the temperature of -30° C
  6. stirringThe mixture was stirred for 30 minutes
  7. additionwas added
  8. stirringby stirring for 1 hour
  9. filtrationThe resultant precipitate was recovered by filtration
  10. washwashed with 50% methanol and dichloromethane
  11. customdried

Sources & evidence

ORD record
ord-82ce362184d446e1bc7717c9949c9079
Source dataset
uspto-grants-1978_01
Patent number
US04068071

Reaction notes

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