Abstract
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.
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Keiko, N.A., Stepanova, L.G., Sarapulova, G.I. et al. The kinetics and mechanism of cyclodimerization of alkylthiopropenals. Russian Chemical Bulletin 49, 1977–1980 (2000). https://doi.org/10.1023/A:1009507522009
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DOI: https://doi.org/10.1023/A:1009507522009