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Australian Journal of Chemistry Australian Journal of Chemistry Society
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RESEARCH ARTICLE

A theoretical study of the chemisty of Furan, Phrrole, Benzofuran, Indole, Dibenzofuran, and Carbazole

RD Brown and AW Coller

Australian Journal of Chemistry 12(2) 152 - 165
Published: 1959

Abstract

It is shown that it is possible, within the framework of the simple Hückel molecular- orbital method, to account fully for all observations on electrophilic substitution in furan, pyrrole, benzofuran, indole, dibenzofuran, and carbazole, in terms of the π-electron distributions in these compounds. The values of coulomb parameters required to obtain this correlation are physically reasonable and in particular are in agreement with values found independently by a variable electronegativity self-consistent field calculation on pyrrole. The previously puzzling difference in orientation of substitution in benzofuran and indole is accounted for in the present study in terms of a difference in the auxiliary inductive effects of the two hetero-atoms. It seems possible to attribute this difference ultimately to differences in the CO and CN bond lengths and to differences in the effective nuclear charges for 2pπ atomic orbitals on the two hetero-atoms. Attention is drawn to an " isoprotonic principle " for estimating the value of the primary coulomb parameter of a hetero-atom. (It is probably a special case of a more general principle-that the primary coulomb parameter is predominantly determined by the charge on the core and scarcely depends upon the nature of the nucleus at the centre of the core.) A spurious Hückel molecular-orbital model for the oxygen heterocycles is noted. It accounts for the chemistry of the heterocycles but represents a physically unsatisfactory view of the electronic properties of oxygen in these compounds.

https://doi.org/10.1071/CH9590152

© CSIRO 1959

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