Reconsideration of solvent effects calculated by semiempirical quantum chemical methods

✍ Scribed by Miroslaw Szafran; Mati M. Karelson; Alan R. Katritzky; Jacek Koput; Michael C. Zerner

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 621 KB
• Volume: 14
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540140312

✦ Synopsis

AM1 and PM3 semiempirical calculations are reported for the solvent effects on the tautomeric equilibria of 2-pyridonel2-hydroxypyridine and 4-pyridone/4-hydroxypyridine in the gas phase and solution. The solvent effects on the tautomeric equilibria were investigated by self-consistent reaction field (SCRF) theory implemented in the AMPAC and MOPAC program in two different ways: one in which all the solvent relaxation is included in the quantum mechanics and the total energy must be corrected for the solvent change in energy, method A; and a second in which the quantum mechanics directly includes this term, method B. The calculated (AMl, method A) tautomeric equilibrium constants (log K,) for 2-pyridone in the gas phase, cyclohexane, chloroform, and acetonitrile are -0.3,0.3, 0.8, and 1.3, respectively, in good agreement with the experimental data ( -0.4.0.24.0.78, and 2.17, respectively). For 4-pyridone/4-hydroxypyridine differences between calculated log K, for the gas phase, chloroform and acetonitrile ( -6.0, -2.6, and -1.2, respectively) and experimental data ( < -1, 0.11, and 0.66, respectively) are larger but the experimental values are also less certain. The experimental acetonitrile data are disturbed by specific interactions. An extension of the SCRF for aqueous solutions is reviewed.