Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Transmission of Substituent Effects through Five-Membered Heteroaromatic Rings. III. Addition Equilibria of Hydroxide Anion to Benzaldehyde Analogues

  • Published : 20001200
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Abstract

Transmission of substituent effects through 5-membered heteroaromatic rings is investigated theoretically at the RHF/6-31+G and B3LYP/6-31+G levels using the equilibria for the $OH^- addition to five-membered heteroaromatic aldehydes (5MHA). The transmission efficiency (S) in 5MHA(A) increases in the order NH>O>S>PH but the order exactly reverses in 5MHA($T^-$). This is originated by the delocalizability of the ${\pi}$ lonepair on Y, $$n_\pi$(Y)$. A better correlation is obtained with ${\sigma}_p^-$ in the Hammett plots with positive slope, $p_z$ > 0, indicating that the substituent (Z) effects are not transmitted by a direct conjugation. The magnitude of $p_z$ for Y=NH is the largest among the heteroaromatic systems, which is consistent with the largest transmission efficiency change $({\Delta}S)$. The equilibria for the addition processes are favorable in the gas phase $({\Delta}G^o<0)$, which reverses to unfavorable in aqueous solution $({\Delta}G^o>0)$ due to the relatively large salvation energy of $OH^-$ in the initial state in aqueous solution. The orders of ${\Delta}G^o$ and $p_z$ in the gas phase are almost maintained in solution.

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References

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