caa a22 4500 60551206X CHVBK 20210128100654.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s00894-015-2606-4 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2606-4 The DFT study on the reaction between benzaldehyde and 4-amine-4H-1,2,4-triazole and their derivatives as a source of stable hemiaminals and schiff bases. Effect of substitution and solvation on the reaction mechanism [Elektronische Daten] [Slawomir Berski, Agnieszka Gordon, Leszek Ciunik] Reaction mechanism for the benzaldehyde (ald) and 4-amine-4H-1,2,4-triazole (4at) has been investigated at the DFT (B3LYP)/6-31+G(d) computational level. Three transition states (TS) have been identified. The TS1 corresponds to hydrogen transfer from the NH2 group to the C = O bond and nucleophillic attack of the carbon atom from the aldehyde group on the nitrogen atom from the NH2 group in 4at. The result of this reaction is the hemiaminal molecule. The TS2 characterises an internal rearrangement of the benzene and triazole rings in the hemiaminal molecule. The TS3 leads to breaking of the O-H bond, the elimination reaction of the H2O molecule, and formation of the C=N bond. The final product of this reaction is a Schiff base. In order to determine the most favorable conditions for hemiaminal formation, the influence of electronic structure modification on the energetic properties during the reaction of benzaldehyde and 4-amine-4H-1,2,4-triazole has been studied. Thirteen substituents: NH2, OH, OCH3, CH3, F, I, Cl, Br, COH, COOH, CF3, CN, NO2, with different Hammett's constant values (σ = −0.66-+0.78) have been considered. Finally, the reaction mechanism has been investigated in the presence of 1 to 5 water molecules. Graphical Abstract The R substituent effect on the energetics of the reaction between (modified) benzaldehyde (R-ald) and 4-amine-4H-1,2,4-triazole Springer-Verlag Berlin Heidelberg, 2015 Bonding nationallicence DFT nationallicence ELF nationallicence Hammett constant nationallicence Hemiaminal nationallicence Mechanism nationallicence Schiff nationallicence Substituent nationallicence Berski Slawomir Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut Gordon Agnieszka Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut Ciunik Leszek Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-17 1610-2940 21:3<1 2015 21 894 https://doi.org/10.1007/s00894-015-2606-4 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2606-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Berski Slawomir Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut NATIONALLICENCE 700 1- Gordon Agnieszka Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut NATIONALLICENCE 700 1- Ciunik Leszek Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383, Wroclaw, Poland aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/3(2015-03-01), 1-17 1610-2940 21:3<1 2015 21 894