Substituent effect on local aromaticity in mono and di-substituted heterocyclic analogs of naphthalene

摘要

A quantitative study on local aromaticity has been performed on a series of mono- and di-substituted biheterocycles (quinoline, isoquinoline, quinoxaline, quinazoline). Three electronically based indices (PDI, ATI, and FLU) have been employed to investigate the substituent effect on the pi-electron delocalization in both heterocycle and benzenoid rings. Three typical substituents (Cl, OCH3, and CN) with different inductive and resonance power have been selected. Generally, substituent causes a reduction in aromaticity irrespective of whether it is electron attracting or electron donating. It is shown that the maximum aromaticity exhibits a similar trend of Cl > CN > OCH3 for all the studied rings. Moreover, it is found that the substituent situation with respect to the heteroatom has a significant influence on the aromaticity. It results from our study that in di-substituted derivatives, irrespective of whether the two substituents form a meta or para isomer, they preferably choose the position which leads to the maximum aromaticity character. Copyright (C) 2009 John Wiley & Sons, Ltd.