反应 #355180

ord-f759e12b51c94cd484dcdffb329cb362

反应方程式

[N-]=C=O
isocyanate
CC1(C)S[C@@H]2[C@H](NC(=O)[C@H](N)c3ccccc3)C(=O)N2[C@H]1C(=O)O
ampicillin
CC1(C)S[C@@H]2[C@H](NC(=O)[C@H](N)c3ccccc3)C(=O)N2[C@H]1C(=O)O
ampicillin
[N-]=C=O
isocyanate
CCO[PH](=O)[N-]OCc1ccccc1
benzyloxy(ethoxy) phosphinylamide
O=C(Cl)Cl
phosgene
CC1(C)S[C@@H]2[C@H](NC(=O)Cc3ccccc3)C(=O)N2[C@H]1C(=O)[O-].[K+]
penicillin
[Na]
sodium
CCOP(=O)(N=C=O)OCc1ccccc1
benzyloxy (ethyloxy)phosphinyl isocyanate

反应条件

详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    其他followed by in vacuo removal of solvents
  2. 2
    其他In the mean time, a solution was prepared in the usual manner
  3. 3
    workup.ADDITIONwas added in 5 minutes
  4. 4
    其他followed by in vacuo removal of dichloromethane
  5. 5
    workup.ADDITIONEthyl acetate was added
  6. 6
    其他The layers were separated
  7. 7
    萃取extraction
  8. 8
    萃取was extracted
  9. 9
    洗涤The combined extracts were washed with iced water
  10. 10
    干燥dried over anhydrous magnesium sulfate
  11. 11
    浓缩concentrated in vacuo to small volume whereupon sodium α-ethylcapronate
  12. 12
    workup.ADDITIONwas added
  13. 13
    其他etc to obtain 8.0 g (62%) of the

实验过程

A solution of crude benzyloxy (ethyloxy)phosphinyl isocyanate [(C6H5CH2O) (C2H5O)P(O)-NCO] in 30 ml of dry dichloromethane was prepared by reaction of 30 mmol of crude benzyloxy(ethoxy) phosphinylamide [(C6H5CH2O) (C2H5 0)P(O)--NH2 ] with phosgene in toluene in the presence of pyridine followed by in vacuo removal of solvents. According to an IR spectrum, the solution contained approximately 20 mmol of the isocyanate. In the mean time, a solution was prepared in the usual manner starting from 7.0 g (20 mmol) of D(-) ampicillin, 5.0 ml of BSA and 30 ml of dichloromethane. This solution was cooled down to 0°C whereupon the solution of the isocyanate was added in 5 minutes and according to thin-layer chromatograms, ampicillin was about two thirds converted into the desired penicillin. The reaction mixture was poured in iced water of pH 7.0, followed by in vacuo removal of dichloromethane. Ethyl acetate was added and the pH lowered to 3.5. The layers were separated and extraction was continued until the greatest part of the penicillin was extracted. The combined extracts were washed with iced water, dried over anhydrous magnesium sulfate, concentrated in vacuo to small volume whereupon sodium α-ethylcapronate was added, etc to obtain 8.0 g (62%) of the above named sodium salt in good state of purity.

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US03945994uspto-grants-1976_03