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Title of Journal: Theor Chem Acc

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Abbravation: Theoretical Chemistry Accounts

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Springer Berlin Heidelberg

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10.1007/s10006-005-0608-6

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1432-2234

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Revisiting the Kolbe–Schmitt reaction of sodium 2

Authors: Svetlana Marković Igor Đurović Zoran Marković
Publish Date: 2015/03/26
Volume: 134, Issue: 4, Pages: 45-
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Abstract

The mechanism of the carboxylation reaction of sodium 2naphthoxide NaphONa was investigated in the positions 1 3 and 6 by means of three methods B3LYP B3LYPD2 and M062X While B3LYP failed to describe reaction pathways 3 and 6 B3LYPD2 owing to the empirical correction term and M062X owing to the way it has been parameterised produced relatively consistent results which create completely new picture of the reaction mechanism It was found that the reactants can build two NaphONa–CO2 complexes of which only one can be further transformed to the reaction products In this new NaphONa–CO2 complex the CO2 moiety is perfectly positioned to perform electrophilic attacks on all three nucleophilic carbons of the naphthalene ring Each reaction pathway occurs via two transition states and one intermediate The mechanism involves a bimolecular reaction step for proton transfer which requires notably smaller activation barrier than previously considered intramolecular rearrangement It was shown that reaction pathway 6 is unfavourable from both kinetic and thermodynamic points of view On the other hand pathways 1 and 3 are competitive pathway 1 requires lower activation barriers but pathway 3 yields the most stable reaction product These thermochemical results are in good agreement with the experimentally determined products ratio

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