@article{KlinkaImrichDaniheletal.2005,
  author    = {Klinka, Karel D. and Imrich, Jan and Danihel, I. and Bohm, Stanislav and Kristian, Pavol and Harnul'akova, S. and Pihlaja, Kalevi and Koch, Andreas and Kleinpeter, Erich},
  title     = {Configuration and E/Z interconversion mechanism of O(S)-allyl-S(O)-methyl-N-(acridin-9-yl)iminothiocarbonate},
  issn      = {0749-1581},
  year      = {2005},
  abstract  = {The configuration and dynamic behavior of O-allyl-S-methyl-N-(acridin-9-yl)iminothiocarbonate (1) and its S- allyl-O-methyl regioisomer (2) were studied using quantum chemical calculations and by applying a novel graphical method to scatter maps obtained from MD simulations for evaluation of an NOE-weighted internuclear distance (r(NOE)). Energy calculations indicated that the Z configuration was predominant for each compound and, further, this was supported both by the calculated chemical shifts and the rNOE. Both N-inversion- and rotation-type transition-state structures were also calculated for the E/Z isomerization process, the results indicating that the preferred interconversion mechanism for 1 is N-inversion, but contrastingly, interconversion via rotation is equally as probable as N-inversion for 2. This supports the notion that one or the other or both pathways can be active and each system needs to be assessed on a case- by-case basis. Copyright (c) 2005 John Wiley \& Sons, Ltd},
  language  = {en}
}
@article{BoehmTomaszcikovaImrichetal.2009,
  author    = {B{\"o}hm, Stanislav and Tomaszcikov{\´a}, Jana and Imrich, J{\´a}n and Danihel, Ivan and Kristian, Pavol and Koch, Andreas and Kleinpeter, Erich and Klika, Karel D.},
  title     = {Computational study to assign structure, tautomerism, E/Z and s-cis/s-trans isomerism, pi-delocalization, partial aromaticity, and the ring size of 1,3-thiazolidin-4-ones and 1,3-thiazin-4-ones formed from thiosemicarbazides},
  issn      = {0166-1280},
  year      = {2009},
  abstract  = {A set of structures encompassing 1-(9-acridinyl)thiosemicarbazide and its 2-methyl derivative together with their various tautomeric structures; the 5-membered ring 1,3-thiazolidin-4-one products resulting from the reaction of 1- (9-acridinyl)thiosemicarbazide and its 2-methyl derivative with dimethyl acetylenedicarboxylate (DMAD) together with the alternative 6-membered ring isomeric reaction products as well as other potential isomeric structures; and the 6- membered ring 1,3-thiazin-4-one product resulting from the reaction of 2-methyl-1-(9-acridinyl)thiosemicarbazide with methyl propiolate (MP) together with the alternative 5-membered ring isomeric reaction product were all extensively studied by molecular modeling calculations using DFT at the B3LYP/6-31G(d,p) level of theory. The ring-chain tautomerism of the thiosemicarbazides, the regio- and stereoselectivity of the reactions, the adopted conformations and E/Z configurations of the products, the prototropic tautomerism of all the compounds, and the reasons for the predominance of the s-cis conformation of the Z configuration of the 1,3-thiazolidin-4-one product in particular were all extensively analyzed. Comparison of the modeled structures were also made to the 1,3-thiazolidin-4-one and 1,3-thiazin-4-one structures of the methyl derivative as well as 1-(9-acridinyl)thiosemicarbazide available from X-ray crystallographic analysis. Tactics utilizing spectroscopic methods {IR frequencies (;) and NMR chemical shifts (;), scalar coupling constants (J), and NOEs (;)} in conjunction with molecular modeling calculations of the spectral parameters {frequency calculations (;) and NMR ; using the GIAO method and J by calculation of the Fermi contact term} were evaluated in terms of proving 5- or 6-membered ring formation.},
  language  = {en}
}
@article{BoehmTomašcikovaImrichetal.2009,
  author    = {Boehm, Stanislav and Tomašcikov{\´a}, Jana and Imrich, J{\´a}n and Danihel, Ivan and Kristian, Pavol and Koch, Andreas and Kleinpeter, Erich and Klika, Karel D.},
  title     = {Computational study to assign structure, tautomerism, E/Z and s-cis/s-trans isomerism, pi-delocalization, partial aromaticity, and the ring size of 1,3-thiazolidin-4-ones and 1,3-thiazin-4-ones formed from thiosemicarbazides},
  issn      = {0166-1280},
  doi       = {10.1016/j.theochem.2009.09.019},
  year      = {2009},
  abstract  = {A set of structures encompassing 1-(9-acridinyl)thiosemicarbazide and its 2-methyl derivative together with their various tautomeric structures; the 5-membered ring 1,3-thiazolidin-4-one products resulting from the reaction of 1- (9-acridinyl)thiosemicarbazide and its 2-methyl derivative with dimethyl acetylenedicarboxylate (DMAD) together with the alternative 6-membered ring isomeric reaction products as well as other potential isomeric structures; and the 6- membered ring 1,3-thiazin-4-one product resulting from the reaction of 2-methyl-1-(9-acridinyl)thiosemicarbazide with methyl propiolate (MP) together with the alternative 5-membered ring isomeric reaction product were all extensively studied by molecular modeling calculations using DFT at the B3LYP/6-31G(d,p) level of theory. The ring-chain tautomerism of the thiosemicarbazides, the regio- and stereoselectivity of the reactions, the adopted conformations and E/Z configurations of the products, the prototropic tautomerism of all the compounds, and the reasons for the predominance of the s-cis conformation of the Z configuration of the 1,3-thiazolidin-4-one product in particular were all extensively analyzed. Comparison of the modeled structures were also made to the 1,3-thiazolidin-4-one and 1,3-thiazin-4-one structures of the methyl derivative as well as 1-(9-acridinyl)thiosemicarbazide available from X-ray crystallographic analysis. Tactics utilizing spectroscopic methods {1R frequencies (nu) and NMR chemical shifts (delta), scalar coupling constants (J), and NOEs (eta)} in conjunction with molecular modeling calculations of the spectral parameters (frequency calculations (v) and NMR 6 using the GIAO method and J by calculation of the Fermi contact term) were evaluated in terms of proving 5- or 6-membered ring formation.},
  language  = {en}
}