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Quantification of the push–pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C bond

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2016
Authors
Rašović, Aleksandar
Blagojević, Vladimir A.
Baranac Stojanović, Marija
Kleinpeter, Erich
Marković, Rade
Minić, Dragica M.
Article (Published version)
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Abstract
Information about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea ...and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.

Keywords:
2-alkylidene-4-oxothiazolidines / NMR / C-C bond / push-pull effect
Source:
New Journal of Chemistry, 2016, 40, 6364-6373
Publisher:
  • Royal Society of Chemistry
Projects:
  • Experimental and theoretical study of reactivity and biological activity of stereodefined thiazolidines and their synthetic analogues (RS-172020)

DOI: 10.1039/c6nj00901h

ISSN: 1144-0546 (Print); 1369-9261 (Online)

WoS: 000385869600088

Scopus: 2-s2.0-84979060401
[ Google Scholar ]
6
2
URI
http://dais.sanu.ac.rs/123456789/2324
Collections
  • ITN SANU - Opšta kolekcija / ITS SASA - General collection
Institution
Институт техничких наука САНУ / Institute of Technical Sciences SASA

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