caa a22 4500 475760115 CHVBK 20180406123548.0 cr unu---uuuuu 170329e20000301xx s 000 0 eng 10.1007/BF02494767 doi (NATIONALLICENCE)springer-10.1007/BF02494767 Multiple bond migration with participation of a protophilic agent [Elektronische Daten] 4. Double bond migration in 3-methylthioprop-1-ene and 3-methoxyprop-1-ene: a comparative study [V. Kobychev, N. Vitkovskaya, E. Larionova, N. Klyba, B. Trofimov] Ab initio study of the pathways of migration of the double bond in the 3-methylthioprop-1-ene (1) and 3-methoxyprop-1-ene (2) molecules with participation of hydroxide ion was carried out by the RHF/6-31+G* and MP2/6-31+G//RHF/6-31+G* methods. Conformational isomerism of the initial molecules and reaction products was considered. The distinctions are discussed in the spatial and electronic structure of intermediate carbanions stabilized (for1) due to the negative hyperconjugation. Stationary points corresponding to complexes between the molecules under study and the hydroxide ion and between the corresponding carbanion and water molecule were localized on the potential energy surfaces of the proton transfer reactions. For2, the single-stage mechanism of prototropic rearrangement involving the H atom of the hydroxide ions was found to be more energetically preferable than the two-stage mechanism, whereas both mechanisms are expected to be equiprobable for1. Kluwer Academic/Plenum Publsihers, 2000 3-methylthioprop-1-ene nationallicence 3-methoxyprop-1-ene nationallicence acidity nationallicence 1,3-hydrogen shift nationallicence hydroxide ion nationallicence reaction mechanism nationallicence potential energy surface nationallicence ab intitio quantum-chemical calculations nationallicence Kobychev V. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Vitkovskaya N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Larionova E. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Klyba N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut Trofimov B. Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/3(2000-03-01), 408-414 1066-5285 49:3<408 2000 49 11172 https://doi.org/10.1007/BF02494767 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02494767 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Kobychev V. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Vitkovskaya N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Larionova E. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Klyba N. Irkutsk State University, 1 ul. K. Marksa, 664003, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Trofimov B. Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/3(2000-03-01), 408-414 1066-5285 49:3<408 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer