Theoretical Study of Reactivities Based on Reactive Hybrid Orbital Analysis. Electrophilic Aromatic Substitution Reactions.
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Accession number;04A0436014
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| Title;Theoretical Study of Reactivities Based on Reactive Hybrid Orbital Analysis. Electrophilic Aromatic Substitution Reactions. |
| Author;
HIRAO HAJIME
(Univ. Tokyo, Graduate School, JPN)
OWADA TOMOHIKO
(Univ. Tokyo, Graduate School, JPN)
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Journal Title;Nippon Kagakkai Koen Yokoshu
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Journal Code:S0493A
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ISSN:0285-7626
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VOL.84th;NO.1;PAGE.9(2004)
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| Figure&Table&Reference;FIG.3, REF.1 |
| Pub. Country;Japan |
| Language;Japanese |
| Abstract;Orbital interactions in electrophilic aromatic substitution reactions of anisol, nitrobenzene, and some other analogues were studied. A single frontier molecular orbital (FMO) does not account for the regioselectivities of the reaction. We herein define the reactive hybrid orbital (RHO) method for measuring reactivity of each carbon atom of substituted benzene. An RHO is made by combining all occupied molecular orbitals properly so that the reactivity index for a reaction center, which is similar to superdelocalizability, is maximized. The RHO reactivity indices,.lamdaoc,.rhooc, and.rho'oc, were shown to predict correctly the experimentally observed regioselectivity and reactivity in the electrophilic aromatic substitution reactions of anisol, nitrobenzene, and other mono-substituted benzenes. Moreover, it was shown that the RHO values for carbon atoms in a polycyclic aromatic hydrocarbon are in good agreement with experimentally determined partial rate factors. (author abst.) |
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