caa a22 4500 475759974 CHVBK 20180406123548.0 cr unu---uuuuu 170329e20001201xx s 000 0 eng 10.1023/A:1009507522009 doi (NATIONALLICENCE)springer-10.1023/A:1009507522009 The kinetics and mechanism of cyclodimerization of alkylthiopropenals [Elektronische Daten] [N. Keiko, L. Stepanova, G. Sarapulova, A. Vashchenko, L. Larina, E. Funtikova, M. Voronkov] The kinetics of 2-alkylthiopropenals cyclodimerization was studied in the temperature range from -7 to +42 °C in heptane and at 20 °C in various solvents. The rate constants for cyclodimerization of 2-alkylthiopropenals are four orders of magnitude higher than those for dimerization of the oxygen-containing analogs, 2-alkoxypropenals, and are independent of the solvent polarity and substituent steric constant. The activation parameters for 2-butylthiopropenal cyclodimerization were estimated. The distribution of electron density in the 2-methoxy- and 2-methylthiopropenals molecules was calculated by the ab initio method. From comparison of the HOMO and LUMO energies for these aldehydes it was concluded that the ratio between the cyclodimerization rates for 2-alkylthio-, 2-ethoxypropenals, and propenal is determined by the HOMO-LUMO gap. Plenum Publishing Corporation, 2000 2-alkylthiopropenals nationallicence Diels-Alder reaction nationallicence kinetics nationallicence reaction mechanism nationallicence 2,5-dialkylthio-3,4-dihydro-2 H -pyran-2-carbaldehyde nationallicence IR spectroscopy nationallicence ab initio calculations nationallicence Keiko N. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Stepanova L. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Sarapulova G. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Vashchenko A. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Larina L. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Funtikova E. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Voronkov M. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/12(2000-12-01), 1977-1980 1066-5285 49:12<1977 2000 49 11172 https://doi.org/10.1023/A:1009507522009 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1023/A:1009507522009 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Keiko N. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Stepanova L. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Sarapulova G. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Vashchenko A. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Larina L. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Funtikova E. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 700 1- Voronkov M. Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/12(2000-12-01), 1977-1980 1066-5285 49:12<1977 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer