ELECTROLYTIC OXIDATION OF URIC ACID: PRODUCTS AND MECHANISM. Report No. 81
Alloxan is the dominant product of the chemical oxidation of uric acid under strongly acid conditions; allantoin is the corresponding product for less acidic to alkaline conditions; separate reaction paths have generally been postulated to account for this difference. A study of the electrolytic oxidation of uric acid indicates the presence of a common path which eventually diverges to produce both alloxan and allantoin in comparable amounts, Uric acid gives a well- defined anodic voltammetric wave at a graphite electrode. When uric acid is electrolytically oxidized in diIute acetic acid at large graphite electrodes, 2.2 Faradays are passed, and 0,25 mole CO/sub 2/, 0.25 mole of a precursor of allantoin, 0.75 mole urea, 0,3 mole parabanic acid and 0.3 mole alloxan simultaneously appear per mole of uric acid oxidized. At any stage during electrolysis, the sum of the moles of allantoin precursor and urea equals the moles of uric acid oxidized. This material balance and the stability of the allantoin precursor indicate that the production of urea is associated with the pathway(s) that produce alloxan and parabanic acid. These and other facts indicate a mechanism whereby uric acid is oxidized in a 2e process to a primary short-lived intermediate, which undergoes three simultaneous transformations: (1) hydrolysis to the allantoin precursor, (2) hydrolysis to alloxan and urea, and (3) further oxidation and hydrolysis leading to parabanic acid and urea. The non- stoichiometric amount of CO/sub 2/ produced and the non-integral number of electrons involved are accounted for by the formation of parabanic acid. The primary oxidation intermediate ultimately produces both allantoin and alloxan, suggesting that this intermediate may be common to all uric acid oxidations and that the ultimate product heretofore considered to be typified by either allantoin or alloxan (but not both) is most likely controlled by experimental conditions. (auth)
- Research Organization:
- Michigan. Univ., Ann Arbor. Dept. of Chemistry
- NSA Number:
- NSA-18-015710
- OSTI ID:
- 4075429
- Report Number(s):
- TID-20253
- Country of Publication:
- United States
- Language:
- English
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