Quantification of the push–pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the CC bond

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 CC 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 CC 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 E_a 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 CC bond lengths and corroborate the applicability of ΔG^‡ for estimation of the strength of the push–pull effect in these and related systems.