Polarographic study of uracil derivatives

Abstract

Eighteen uracil derivatives were studied by d.c. polarography, differential-pulse (d.p.)polarography and d.p. cathodic stripping voltammetry. In a borax buffer at ca. pH 7.6, uracil, thymine and derivatives such as 5-halouracils, 5-trifluoromethyl-,5-aza-,5-acetyl-, 5-formyl- and 5-vinyl-uracil produced well-defined peaks at potentials between 0 V and ca. 160 mV vs. silver/ silver chloride (satd. KCl). The peaks are ascribed to the formation of sparingly soluble mercury salts. For the other derivatives tested (e.g., 5-nitro- and 5-ethynyl-uracil and 6-substituted uracils), the peaks were less well-defined and in some cases the polarographic curves were very complex. 2-Thiouracil produced a single peak at ca. −400 mV, but only at pH 12.2. The shapes, heights and potentials of the peaks depended on the kind and position of the substituent on the pyrimidine ring. Rectilinear relationships of peak current vs. concentrations were found for most compounds (10 −5-10 −4 M) by d.p. polarography; d.c.polarography was not tested quantitatively. For 5-fluorouracil and 5-vinyluracil, linear calibrations were found for concentrations of 0.5–5 × 10 −7 M by d.p. cathodic stripping voltametry. Interference studies showed that small amounts of chloride and phosphate did not interfere but 5-fluorodeoxyuridine, which did not itself produce a peak, and proteins interfered seriously.