Potassium Bromide → Clavulanic Acid

HRID 637280Notes

Reaction equation

HRID 637280 reaction equation
[CH2:1]1[C:4](=[O:5])[N:3]2[C@@H:6]([C:12]([O:14]CC3C=CC=CC=3)=[O:13])/[C:7](/[O:11][C@H:2]12)=[CH:8]/[CH2:9][OH:10].C(=O)(O)[O-].[Na+].[K+].[Br-]>C(O)C.O.[Pd]>[CH2:1]1[C:4](=[O:5])[N:3]2[C@@H:6]([C:12]([OH:14])=[O:13])/[C:7](/[O:11][C@H:2]12)=[CH:8]/[CH2:9][OH:10]

Participants

7

Reactant 3

HCID 253877Potassium BromideHCID 516892Sodium BicarbonateHCID 99040553-(2-Hydroxy-ethylidene)-7-oxo-4-oxa-1-aza-bicyclo[3.2.0]heptane-2-carboxylic acid benzyl ester(benzyl calvunlanate)

Product 1

HCID 5280980Clavulanic Acid

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

Benzyl clavulanate (840 mgs) in ethanol (30 ml) and water (5 ml) was hydrogenated over 10% Pd/C (267 mgs) and sodium bicarbonate (244 mgs) for 25 minutes at room temperature and atmospheric pressure. The catalyst was filtered, washed with water and ethanol and the combined filtrates were evaporated in vacuo. The product crystallised from a water-acetone mixture as microneedles (565 mgs). Recrystallisation from water-acetone gave needles which, after drying over P2O5 in vacuo for 24 hours gave the following analysis: C 41.01, 40.86; H 3.77, 3.64; N 5.68, 5.51; i.r. (KBr disc) 1785, 1700, 1620 cm-1 ; Nmr (D2O) 3.06 (d,1,J=18.5 Hz), 3.57 (dd,1,J1 =18.5 Hz, J2 =2.5 Hz), 4.15 (d,2,J=8 Hz), 5.3 (HOD), 4.9(m), 5.71 (d,1,J=2.5 Hz).

Workup

  1. filtrationThe catalyst was filtered
  2. washwashed with water and ethanol
  3. customthe combined filtrates were evaporated in vacuo
  4. customThe product crystallised from a water-acetone mixture as microneedles (565 mgs)
  5. customRecrystallisation from water-acetone
  6. customgave needles which
  7. dry with materialafter drying over P2O5 in vacuo for 24 hours
  8. customgave the following analysis

Sources & evidence

ORD record
ord-20f320862ff54c9fbba44962cd863467
Source dataset
uspto-grants-1985_12
Patent number
US04556559

Reaction notes

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