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Theoretical study concerning the reactivity of imine derivatives of polycyclic aromatic hydrocarbons
Author(s) -
Borosky Gabriela L.
Publication year - 2003
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10197
Subject(s) - imine , chemistry , protonation , reactivity (psychology) , computational chemistry , polycyclic aromatic hydrocarbon , aromaticity , carbocation , delocalized electron , polycyclic compound , molecular orbital , photochemistry , medicinal chemistry , organic chemistry , molecule , catalysis , medicine , ion , alternative medicine , pathology
The opening reaction of N ‐protonated polycyclic aromatic hydrocarbon imines has been computed by means of ab initio , density functional, and semiempirical methods of calculation. Imines are predicted to be more stable than the corresponding O‐protonated derivatives, epoxides and diol epoxides. On the other hand, the activated N ‐methanesulfonylbenzene imine presented more favorable Δ E ≠ and Δ E r for ring opening due to the effect of hydrogen‐bond interactions. Anti and syn trans ‐diol benzene imines did not show a different behavior from the unsubstituted imine. According to these calculations, bay‐region, fjord‐region, and bay‐region methyl‐substituted compounds opened more easily among the imine derivatives, following the same reactivity pattern as the oxygen analogs. The exothermicity of the opening process correlated with the charge delocalization in the resulting carbocation. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 601–608, 2003