Pyridone cations, tautomerism

Proton resonance spectroscopy has been used to study the tautomerism of 4-hydroxypyridine and its 1-oxide, with results in agreement with those obtained by other physical methods discussed here. Resonance spectroscopy also indicated that the cations of 4-hydroxypyridine, 1-methyl-4-pyridone and 4-methoxypyridine are of the type (32), that of 4-hydroxy-pyridine 1-oxide as (33), and that 2-pyridone cation is protonated on... 

Recently, zero kinetic energy (ZEKE) photoelectron spectroscopy has been used to study the OH/NH tautomerism of 2-pyridone in the gas phase (95JPC8608). This work, which is expected to develop considerably, provides a wealth of information about that equilibrium for the states So, Sj, and Do (cation ground state). 

Hydroxy pyridine 1-oxides are also tautomeric the 4-isomer exists in about equal amounts of forms (783) and (784). 4-Hydroxy-pyrones and -pyridones exhibit a different type of tautomerism the a-one (e.g. 785) structure is favored relative to the y-one structure. (3-Hydroxy-4-pyrones such as kojic acid (786) show phenolic properties (CHEC 3.28, Scheme 30). a- and 3-Hydroxy cations (e.g. 787) are the conjugate acids of pyridones and pyrones and are considered in the next section. 

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