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Theoretical Study of Molecular Structure, Tautomerism, and Geometrical Isomerism of N-Methyl- and N-Phenyl-Substituted Cyclic Imidazolines, Oxazolines, and Thiazolines

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Abstract

The geometries of various tautomers and isomers of 2-methylamino-2-imidazoline, 2-methylamino-2-oxazoline, 2-methylamino-2-thiazoline, 2-phenylamino-2-imidazoline, 2-phenylamino-2-oxazoline, and 2-phenylamino-2-thiazoline have been studied using the Becke3LYP/6–31+G(d,p) DFT, ONIOM(Becke3LYP/6–31+G(d,p):HF/3–21G*) and ONIOM(Becke3LYP/6–31+G(d,p):AM1) methods. The optimized geometries indicate that these molecules show a distinctly nonplanar configuration of the cyclic moieties. In the gas phase, the amino tautomers (with exception of 2-phenylamino-2-imidazoline) are computed to be more stable than the imino tautomers. Of the two possible (E and Z) isomers of methyl and phenyl derivatives of imino-oxazolidine and imino-thiazolidine species, the (Z) isomers have the lowest energy. The iminozation free energies in the gas phase were found to be 5 – 15 kJ/mol. Absolute values of K T depend strongly on the accuracy of the method used for calculation of free energy. Solvation (using the MD simulations) causes, in most cases, a shift in tautomeric preference toward the imino species.

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Authors and Affiliations

  1. Department of Pharmaceutical Chemistry, Comenius University, SK-832 32, Bratislava, Slovakia

    Milan Remko

  2. Department of Theoretical Chemistry, Materials Science Centre, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands

    Piet Th. Van Duijnen & Marcel Swart

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  1. Milan Remko
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  2. Piet Th. Van Duijnen
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  3. Marcel Swart
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Correspondence to Milan Remko.

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Remko, M., Van Duijnen, P.T. & Swart, M. Theoretical Study of Molecular Structure, Tautomerism, and Geometrical Isomerism of N-Methyl- and N-Phenyl-Substituted Cyclic Imidazolines, Oxazolines, and Thiazolines. Structural Chemistry 14, 271–278 (2003). https://doi.org/10.1023/A:1023811829286

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