A series of N-aryl-3,4-(9′,10′-dihydroanthracene-9′, 10′-diyl)succinimides have been synthesized as model compounds to study the interaction of an aromatic π system with aliphatic H atoms and heteroatoms such as oxygen, sulfur, and fluorine. The steric requirements of the rigid scaffold forces the N-aryl residue and a benzene ring of the dihydroanthracenyl moiety to adopt an edge-to-face conformation in which one of the ortho-substituents of the N-aryl group interacts with the π system. The succinimides were generally obtained as mixtures of isomers and their ratios were considered as a function of the substitution pattern at the ortho positions of the N-aryl residue. The experimentally observed ratios were in good agreement with those predicted computationally by DFT calculations at the BMK/cc-pVDZ level of theory. From this study it was concluded that in these systems the aliphatic C-H/π interaction is mildly stabilizing and, to a certain extent, capable of overcoming unfavorable steric effects. On the other hand, the interaction of a π system with oxygen, sulfur, or fluorine atoms was destabilizing. When methyl or ethyl groups were allowed to compete with oxygen and fluorine for interaction with the benzene ring, C-H/π interactions were consistently observed to preferentially occur despite unfavorable steric effects.
Aliphatic C–H/π and Heteroatom/π Interactions in N-Aryl-3,4-(9′,10′-dihydroanthracene-9′,10′-diyl)succinimides / L. Raimondi, M. Benaglia, F. Cozzi. - In: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. - ISSN 1434-193X. - 2014:23(2014), pp. 4993-4998.
|Titolo:||Aliphatic C–H/π and Heteroatom/π Interactions in N-Aryl-3,4-(9′,10′-dihydroanthracene-9′,10′-diyl)succinimides|
RAIMONDI, LAURA MARIA (Primo)
BENAGLIA, MAURIZIO (Secondo)
COZZI, FRANCO (Corresponding)
|Settore Scientifico Disciplinare:||Settore CHIM/06 - Chimica Organica|
|Data di pubblicazione:||2014|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1002/ejoc.201402288|
|Appare nelle tipologie:||01 - Articolo su periodico|