Ivanovo, Ivanovo, Russian Federation
Ivanovo, Ivanovo, Russian Federation
UDK 547.712.2 Соединения, в молекулах которых циклы непосредственно соединены друг с другом
UDK 544.32 Термодинамические функции химических процессов
UDK 544.582.6 Изотопные эффекты
This review is based on the analysis of data on the structural and thermodynamic properties of tetra-N-alkyl-substituted bicyclic bis-urea of the octane series (glycolurils), singly and dissolved in H2O and D2O, obtained by other authors. The paper discusses issues of the influence of the stereochemical nature of these bioactive compounds on their hydration processes. The researched substances are the low-toxic glycolurils with pharmacologically pronounced psychotropic effects, known under the commercial names Mebicar (tetra-N-methylanalog), Bicaret (tetra-N-ethylanalog), and the cis- and trans-N-diethyl-dimethyl-analogs, Mebicaret and Albicar. The last listed glycoluril, which is chiral in stereochemical nature, was investigated as racemate. The study also included the analysis of the available results of calorimetric, densitometric, and spectroscopic (for Mebicar) studies of glycolurils solutions in H/D isotopologues of water as well as quantum-chemical calculations of molecular parameters of these heterocyclic compounds in the ideal gas phase. It has been shown that the hydration of each of the studied tetra-N-alkyl-substituted glycolurils can be generally regarded as a superposition of two mechanisms – hydrophobic and hydrophilic. In the case of Bicaret, the former is dominant, while for Mebicar the latter obviously predominates. Regarding to the structural state and solvation in aqueous medium of glycolurils with mixed N-alkyl-substitution such as Albicar and Mebicaret, the stereochemical nature of their molecules predetermines a kind of "thermodynamic balance (dualism)" between the mentioned mechanisms. The paper outlines the distinctive features of the hydration process of racemic Albicar against the effects of intermolecular interaction in aqueous solution of achiral Mebicaret.
tetra-N-alkyl-substituted glycoluriles; H/D water isotopologues; standard molar volumes and dissolution enthalpies; solvent isotope effects; molecular parameters; hydrophilic and hydrophobic hydration
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