• Bulletin of the Korean Chemical Society
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• v.22 no.4
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• pp.395-400
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• 2001

The effects of ortho- (R = H and CH3) and Y-substituents (Y = OCH3, CH3H and CN), which are directly attached to the carbonyl carbon, on the protonation equilibria of the para-X-substituted benzoyl derivatives, 4-X -2, 6-di-R-C6H2-C(=O)-Y, are investigated theoretically using the B3LYP method with 6-31+G* basis set. Structurally, both of the (B) and (BH+ ) forms in the species with R = H are nearly coplanar regardless of the Y-substituents implying that the steric repulsion between Y-substituent and R = H is relatively small. In the species with R = CH3 , the tortional angle (Θ) between the carbonyl moiety and aryl ring varies from zero to near right angle depending on the degree of steric repulsion between Y and R = CH3 and the resonance demand. However the reaction energies, ΔG°, for the protonation processes are more favorable for R = CH3 than for R = H due to stronger electron donating effect of R = CH3 , although the species with R = CH3 are unfavorable sterically. On the other hand, the Hammett type plots are progressively better correlated with б+ than with б values on going from Y = OCH3 to Y = CN for both species with R = H and CH3 indicating that the degree of resonance delocalization between carbonyl moiety and X-substituent is increased for a more electron accepting Y-substituent. Nevertheless the effects of R = CH3 on the magnitude of Hammett type reaction constants ( б or б+ ) are not much different from those of R = H.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.882-890
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• 2000

Ab initio calculations are carried out on protonation equilibria of 5-memberedheteroaromatic aldehydes (5MHAs;heteroatom Y = NH, O, PH,and S and substituentZ = NH2, OCH3, SCH3, CH3, H, Cl, CHO, CN,NO2) at the $MP2}6-31G*$ level. Naturalbond orbital (NBO) analyses show that the optimal localized natural Lewis structures of the protonated aldehydes,(P), are ortho (C3) protonated (for Y = O, PH and S) and N-pro-tonated (for Y = NH) forms in contrast to the standard structural Lewis formula for aldehydes, (R). The delo-calizability of ${\pilone}-pairon$ the heteroatom $(n{\pi}(Y))$ is in the order Y = NH > O > S > PH. The transmission efficiency of (Z) substituent effects to the carbonyl moiety run parallel to the delocalizability of $n{\pi}(Y)$ for R,but is dominantly influenced by the cationic charge on $C{\alpha}(C{\alpha}+)$ for P, which is in the reverse order of thede-localizability of $n{\pi}(Y).$ The Hammett ${\rho}values$ for variation of Z in the protonation are determined by the dif-ference in the transmission efficiencies between Pand R stateat simple interpretation of their magnitude is not warranted. However,the magnitude of the gas-phase ${\rho}z+$ values decreases as the level ofcomputation is raised from RHF/3-21G* to RHF/6-31G* and to $MP2}6-31G*$ but increases again at the MP4SDQ/6-31G* level. Further decrease occurs when solvent effect (water) is accounted for by the SCRF method. Comparison of the SCRF ${\rho}z+values$ with those determined in the aqueous acid solution for Y = S and CHCH shows inadequacy of accounting for the solvent effects on the ${\rho}values$ by a continuum model. It is noteworthy that semiempirical calculations, especially theAM1 method, give even lower magnitude of the gas-phase ${\rho}values.

• Bulletin of the Korean Chemical Society
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• v.21 no.9
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• pp.849-854
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• 2000

The protonation and divalent cation complexation equilibria of several quinolone antibiotics such as nalidixic acid (NAL),flumequine (FLU), oxolinic acid (OXO), ofloxacin (OFL), norfloxacin (NOR) and enoxacin (ENO) have been examined by potentiome tric titration and spectrophotometric method. The antibacterial activity of these drugs depends upon the pH and the concentration of metal cations such as Mg2+ , Ca2+ in solu-tion. The apparent ionization constants of NAL, FLU, OXO, OFL, NOR and ENO in aqueous solution were found to be 6.33, 6.51, 6.72, 7.18, 7.26, and 7.53, respectively. In aqueous solution, NAL, FLU and OXO were found to be present mainly as two chemical species : molecularand anionic; but OFL, NOR and ENO were present mainly as three chemical species : anionic, neutral zwitterionic and cationic form, in equilibrium. The pKa1 and pKa2are found to be 6.10 and 8.28 for OFL; 6.23 and 8.55 for NOR; 6.32 and8.62 for ENO, respec-tively. The complex formation constants between OFL, NOR or FLU and some divalent cations are measured at pH 7.5. The 1 : 1 complexes are formed mainly by ion-dipole interaction. FLU has somewhat larger Kf values than OFL and NOR because its molecular size is small and the FLU is present asanionic form at pH 7.5.