Nitroxyl → 6-Aminopenicillanic acid

HRID 1076522Notes

Reaction equation

HRID 1076522 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]([OH:22])=[O:21].[K].CN(C)C1C=CC=CC=1.CP(Cl)(CCCCCCCC)=O.P(Cl)(Cl)(Cl)(Cl)Cl.N=O>C(Cl)Cl.C(O)CCC>[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

8

Reactant 5

HCID 945NitroxylHCID 949N,N-Dimethylaniline2×HCID 24819Phosphorus pentachlorideHCID 53876963Methyl-n-octylphosphinic acid chlorideHCID 66586213CID 66586213

Product 1

HCID 110826-Aminopenicillanic acid

Reagents, catalysts & solvents 2

HCID 2631-ButanolSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-25 °C

Procedure

To a suspension of 14.9 g of penicillin-G-potassium (= 40 mmols) in 60 ml of absolute methylene chloride 10 ml of N,N-dimethylaniline and 8.42 g (= 40 mmols) of methyl-n-octylphosphinic acid chloride were added successively while stirring. After an hour at 0°C the reaction mixture was cooled to -25°C and 9.0 g (= 43 mmols) of phosphorus pentachloride were introduced. After an hour at -25°C, 60 ml of n-butanol and 2 ml of N,N-dimethylaniline were introduced and by after-stirring for an hour at -25°C the iminoether was formed. Then, hydrolysis followed in the manner described in Example 1. 7.47 g (= 88.5 % of the theory) of 6-aminopenicillanic acid having a melting point of 195°C (decomposition) were isolated in the form of colorless crystals, the identity of which was examined in an analogous manner as described in Example 1.

Workup

  1. additionwere added successively
  2. waitAfter an hour at -25°C
  3. customwas formed
  4. customThen, hydrolysis

Sources & evidence

ORD record
ord-2cf404ac9ce345acba3877034472d295
Source dataset
uspto-grants-1976_05
Patent number
US03957771

Reaction notes

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