Conclusions
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1.
The electronic and energy indices of neutral, anionic, bipolar, and cationic forms ofβ-hydroxypyridine were calculated by the molecular orbital method in the Hückel approximation.
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2.
The calculated values of the energy differences between the highest occupied and lowest free molecular orbitals are linearly correlated with the experimental values of the absorption maxima of the long-wave (π →π *) bands of the four forms ofβ-hydroxypyridine.
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3.
The values obtained for the energies of localization indicate that electrophilic substitution forβ-hydroxypyridine proceeds in the sequence 2>6>4>5, also observed experimentally. The sequence 2>6>4>5 has been predicted for nucleophilic and radical substitution.
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4.
A comparison of various indices of reactivity gives a basis for concluding that reactions of electrophilic substitution inβ-hydroxypyridine proceed through the formation of an intermediate σ-complex.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2140–2144, October, 1971.
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Zaitsev, B.E., Grachev, V.T., Dyumaev, K.M. et al. Electronic structure and reactions of aromatic substitution inβ-hydroxypyridine. Russ Chem Bull 20, 2024–2027 (1971). https://doi.org/10.1007/BF00851242
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DOI: https://doi.org/10.1007/BF00851242