Theoretical Study of the Orientation Rules in Photonucleophilic Aromatic Substitutions

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• 作者：B. Pint&eacute ; r ; F. De Proft ; T. Veszpr&eacute ; mi ; P. Geerlings
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：February 15, 2008
• 年：2008
• 卷：73
• 期：4
• 页码：1243 - 1252
• 全文大小：242K
• 年卷期：v.73,no.4(February 15, 2008)
• ISSN：1520-6904

文摘

BLE>bscribe/journals/joceah/73/i04/figures/jo701392mn00001.gif" ALIGN="left" HSPACE=5>The photonucleophilic aromatic substitution reactions of nitrobenzene derivatives were studied by abinitio and Density Functional Theory methods. The photohydrolysis is shown to proceed via an addition-elimination mechanism with two intermediates, except in the case of a chlorine leaving group. Dependingon the substituents, the addition step, the elimination step, or the radiationless transition is the rate-determining process. The solvent effect on the S_N2 Ar* reactions was evaluated by a continuum model.Next, the regioselectivity of the addition step is investigated within the framework of the so-called spin-polarized conceptual density functional theory. It is shown that the preference observed for the meta orpara (with respect to the NO₂ group) pathways in the addition step can be predicted by using the spin-polarized Fukui functions applied for the prereactive -complex.