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TIP Revista Especializada en Ciencias Químico-Biológicas

2014, Number 1

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TIP Rev Esp Cienc Quim Biol 2014; 17 (1)

Efecto electromérico autógeno en el N-óxido de piridina y su nitración

Sánchez-Viesca F, Gómez MR

Language: Spanish
References: 38
Page: 56-61
PDF size: 173.65 Kb.


ABSTRACT

Linton found out that the dipole moment of pyridine N-oxide is appreciably smaller than the expected theoretical value. Thus, he postulated the contribution of three ‘excited structures’, with a negative electric charge at the 2-, 4- and 6-position. However, a typical electrophilic substitution such as nitration, afforded only the 4-nitro derivative. This discrepancy between theory and experiment prompted us to study the pyridine N-oxide physical properties, since its reactivity is derived from them. Besides, these negative charged rings require an unexpected polarization and a reaction mechanism must be provided. We propose intermolecular induced polarization as a viable path. We uncovered that only one of the three structures before mentioned is supported by the observed reactivity and by 13C nuclear magnetic resonance data. On rejecting 2 of the Linton’s ‘excited structures’, we have explained the regioselectivity found in pyridine N-oxide nitration.


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