Reactions of oxidizing radicals with 2- and 3-aminopyridines: a pulse radiolysis study |
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Authors: | G. R. Dey D. B. Naik P. Dwibedy K. Kishore |
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Affiliation: | Applied Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India |
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Abstract: | Reactions of OH radicals and some one-electron oxidants with 2-aminopyridine (2-AmPy) and 3-aminopyridine (3-AmPy) were studied in aqueous solutions using pulse radiolysis technique. The OH adduct of 2-AmPy at pH 9 has an absorption maximum at 360 nm along with a weak absorption band in the visible region and was found to be reactive with oxygen. The rate constant for its reaction with O2 was determined to be 1.0×108 dm3 mol−1 s−1. At pH 4 also, the OH adduct of 2-AmPy has an absorption band at 360 nm. However, there are differences in the absorption at other wavelengths. From the plot of ΔOD vs. pH at 340 nm, the pKa of the OH adduct was determined to be 6.5. Among the specific oxidants, only SO4−√ radicals were able to oxidize 2-AmPy. In the case of 3-aminopyridine (3-AmPy), the transient species formed by OH radical reaction at pH 9 has an absorption maximum at 410 nm with shoulder bands on both the sides. Its absorption spectrum at pH 4 was different indicating the existence of a pK value for the OH adduct. pKa of 3-AmPy-OH radical adduct species was evaluated to be 5.7. This adduct species was also found to be reactive with oxygen (k=7.6×106 dm3 mol−1 s−1). Specific one-electron oxidants like N3√, Br2−√ C2−√ and SO4−√ were able to oxidize 3-AmPy indicating that it is easier to oxidize 3-AmPy as compared to 2-AmPy. |
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Keywords: | 2-aminopyridine 3-aminopyridine Pulse radiolysis Rate constants pKa values |
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