Sodium Hydroxide → 3-Carbamoyloxymethyl-7-amino-3-cephem-4-carboxylic acid

HRID 2049732Notes

Reaction equation

HRID 2049732 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[CH:16]([NH:17]C(OCC3C=CC([N+]([O-])=O)=CC=3)=O)[C:15](=[O:31])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=[O:3])[NH2:2].[OH-].[Na+]>O.[Pd]>[NH2:17][CH:16]1[C:15](=[O:31])[N:10]2[C:11]([C:12]([OH:14])=[O:13])=[C:6]([CH2:5][O:4][C:1](=[O:3])[NH2:2])[CH2:7][S:8][C@H:9]12

Participants

5

Reactant 2

HCID 14798Sodium HydroxideHCID 70581038HCID 70581038, compound

Product 1

HCID 127847593-Carbamoyloxymethyl-7-amino-3-cephem-4-carboxylic acid

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent2×

Procedure

3-Carbamoyloxymethyl-7-p-nitrobenzyloxycarbonylamino-3-cephem-4-carboxylic acid (7.5 g.; 16.5 m. mole) was dissolved in water (100 ml) by adding 1 N sodium hydroxide solution to give a solution with a pH of 7.0. This solution was added to pre-hydrogenated 5% palladium on calcium carbonate catalyst (7.5 g.) in water (100 ml) and hydrogenation was continued for 41/2 hours. The reaction mixture was filtered and the filtrate was washed with ether and freeze dried. Thin layer chromatography of the solid residue in chloroform, acetone, acetic acid (50:50:7) revealed one spot with no starting material present. This residue was dissolved in water (25 ml) and the pH of the solution adjusted to 4.0 with 1 N hydrochloric acid resulting in the precipitation of a white solid. The mixture was cooled in the refrigerator and the white solid was collected and dried in vacuo. (1.954 g.). The filtrate was reduced to 5 ml by evaporation and a second crop of solid (0.320 g.) was obtained on cooling. Both crops were dried in vacuo and characterized as 7-amino-3-carbamoyloxymethyl-3-cephem-4-carboxylic acid. δ (TFA) 5.5 (4H, sharp s on top of AB quartet, H7, H6 and 3-CH2 -); δ (DMSO) 6.58 (2H, s, OCONH2, exchanges with D2O), 5.00 (2H, m, H7 and α-protons), 4.75 (3H, d overlapping AB quartet, H6 and 3-CH2) and 3.50 (2H, broad s, S-CH2) γ max (KBr) 1790 (β-lactam C=O), 1710, 1605 cn-1 ; λ max (H20) 265 nm (εm 7,203).

Workup

  1. customto give a solution with a pH of 7.0
  2. custom2 hours
  3. filtrationThe reaction mixture was filtered
  4. washthe filtrate was washed with ether and freeze
  5. customdried
  6. dissolutionThis residue was dissolved in water (25 ml)
  7. customthe pH of the solution adjusted to 4.0 with 1 N hydrochloric acid resulting in the precipitation of a white solid
  8. temperatureThe mixture was cooled in the refrigerator
  9. customthe white solid was collected
  10. customdried in vacuo
  11. customThe filtrate was reduced to 5 ml by evaporation
  12. customa second crop of solid (0.320 g.) was obtained
  13. temperatureon cooling
  14. customBoth crops were dried in vacuo

Sources & evidence

ORD record
ord-133daadbf44748a4bda09389c29f3703
Source dataset
uspto-grants-1980_04
Patent number
US04198503

Reaction notes

Loading…