Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones
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2013
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The electronic structure of 5-arylidene-2,4-thiazolidinediones has been studied by using experimental and theoretical methodology. The theoretical calculations of the investigated 5-arylidene-2,4-thiazolidinediones have been performed by the use of quantum chemical methods. The calculated C-13 NMR chemical shifts and NBO atomic charges provide an insight into the influence of such a structure on the transmission of electronic substituent effects. Linear free energy relationships (LFERs) have been further applied to their C-13 NMR chemical shifts. The correlation analyses for the substituent-induced chemical shifts (SCS) have been performed with sigma using SSP (single substituent parameter), field (sigma(F)) and resonance (sigma(R)) parameters using DSP (dual substituent parameter), as well as the Yukawa-Tsuno model. The presented correlations account satisfactorily for the polar and resonance substituent effects operative at C-beta. and C-7 carbons, while reverse substituent effect wa...s found for C-alpha. The comparison of correlation results for the investigated molecules with those obtained for seven structurally related styrene series has indicated that specific cross-interaction of phenyl substituent and groups attached at C-alpha carbon causes increased sensitivity of SCS C-beta to the resonance effect with increasing of electron-accepting capabilities of the group present at C-beta.
Ključne reči:
C-13 NMR / Substituent effect / Linear free energy relationships / Yukawa-Tsuno model / Quantum chemical calculationIzvor:
Journal of Molecular Structure, 2013, 1049, 59-68Izdavač:
- Elsevier, Amsterdam
Finansiranje / projekti:
- Proučavanje sinteze, strukture i aktivnosti organskih jedinjenja prirodnog i sintetskog porekla (RS-MESTD-Basic Research (BR or ON)-172013)
DOI: 10.1016/j.molstruc.2013.06.027
ISSN: 0022-2860
WoS: 000324784700009
Scopus: 2-s2.0-84885110669
Institucija/grupa
Tehnološko-metalurški fakultetTY - JOUR AU - Rančić, Milica AU - Trišović, Nemanja AU - Milčić, Miloš AU - Ajaj, Ismail AU - Marinković, Aleksandar PY - 2013 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/2460 AB - The electronic structure of 5-arylidene-2,4-thiazolidinediones has been studied by using experimental and theoretical methodology. The theoretical calculations of the investigated 5-arylidene-2,4-thiazolidinediones have been performed by the use of quantum chemical methods. The calculated C-13 NMR chemical shifts and NBO atomic charges provide an insight into the influence of such a structure on the transmission of electronic substituent effects. Linear free energy relationships (LFERs) have been further applied to their C-13 NMR chemical shifts. The correlation analyses for the substituent-induced chemical shifts (SCS) have been performed with sigma using SSP (single substituent parameter), field (sigma(F)) and resonance (sigma(R)) parameters using DSP (dual substituent parameter), as well as the Yukawa-Tsuno model. The presented correlations account satisfactorily for the polar and resonance substituent effects operative at C-beta. and C-7 carbons, while reverse substituent effect was found for C-alpha. The comparison of correlation results for the investigated molecules with those obtained for seven structurally related styrene series has indicated that specific cross-interaction of phenyl substituent and groups attached at C-alpha carbon causes increased sensitivity of SCS C-beta to the resonance effect with increasing of electron-accepting capabilities of the group present at C-beta. PB - Elsevier, Amsterdam T2 - Journal of Molecular Structure T1 - Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones EP - 68 SP - 59 VL - 1049 DO - 10.1016/j.molstruc.2013.06.027 ER -
@article{ author = "Rančić, Milica and Trišović, Nemanja and Milčić, Miloš and Ajaj, Ismail and Marinković, Aleksandar", year = "2013", abstract = "The electronic structure of 5-arylidene-2,4-thiazolidinediones has been studied by using experimental and theoretical methodology. The theoretical calculations of the investigated 5-arylidene-2,4-thiazolidinediones have been performed by the use of quantum chemical methods. The calculated C-13 NMR chemical shifts and NBO atomic charges provide an insight into the influence of such a structure on the transmission of electronic substituent effects. Linear free energy relationships (LFERs) have been further applied to their C-13 NMR chemical shifts. The correlation analyses for the substituent-induced chemical shifts (SCS) have been performed with sigma using SSP (single substituent parameter), field (sigma(F)) and resonance (sigma(R)) parameters using DSP (dual substituent parameter), as well as the Yukawa-Tsuno model. The presented correlations account satisfactorily for the polar and resonance substituent effects operative at C-beta. and C-7 carbons, while reverse substituent effect was found for C-alpha. The comparison of correlation results for the investigated molecules with those obtained for seven structurally related styrene series has indicated that specific cross-interaction of phenyl substituent and groups attached at C-alpha carbon causes increased sensitivity of SCS C-beta to the resonance effect with increasing of electron-accepting capabilities of the group present at C-beta.", publisher = "Elsevier, Amsterdam", journal = "Journal of Molecular Structure", title = "Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones", pages = "68-59", volume = "1049", doi = "10.1016/j.molstruc.2013.06.027" }
Rančić, M., Trišović, N., Milčić, M., Ajaj, I.,& Marinković, A.. (2013). Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones. in Journal of Molecular Structure Elsevier, Amsterdam., 1049, 59-68. https://doi.org/10.1016/j.molstruc.2013.06.027
Rančić M, Trišović N, Milčić M, Ajaj I, Marinković A. Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones. in Journal of Molecular Structure. 2013;1049:59-68. doi:10.1016/j.molstruc.2013.06.027 .
Rančić, Milica, Trišović, Nemanja, Milčić, Miloš, Ajaj, Ismail, Marinković, Aleksandar, "Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones" in Journal of Molecular Structure, 1049 (2013):59-68, https://doi.org/10.1016/j.molstruc.2013.06.027 . .