Experimental and theoretical study of substituent effect on C-13 NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones
Само за регистроване кориснике
2013
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
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.
Кључне речи:
C-13 NMR / Substituent effect / Linear free energy relationships / Yukawa-Tsuno model / Quantum chemical calculationИзвор:
Journal of Molecular Structure, 2013, 1049, 59-68Издавач:
- Elsevier Science Bv, Amsterdam
Финансирање / пројекти:
- Проучавање синтезе, структуре и активности органских једињења природног и синтетског порекла (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
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - JOUR AU - Rančić, Milica AU - Trišović, Nemanja P. AU - Milčić, Miloš K. AU - Ajaj, Ismail A. AU - Marinković, Aleksandar PY - 2013 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1404 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 Science Bv, 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 VL - 1049 SP - 59 EP - 68 DO - 10.1016/j.molstruc.2013.06.027 ER -
@article{ author = "Rančić, Milica and Trišović, Nemanja P. and Milčić, Miloš K. and Ajaj, Ismail A. 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 Science Bv, 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", volume = "1049", pages = "59-68", doi = "10.1016/j.molstruc.2013.06.027" }
Rančić, M., Trišović, N. P., Milčić, M. K., Ajaj, I. A.,& 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 Science Bv, Amsterdam., 1049, 59-68. https://doi.org/10.1016/j.molstruc.2013.06.027
Rančić M, Trišović NP, Milčić MK, Ajaj IA, 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 P., Milčić, Miloš K., Ajaj, Ismail A., 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 . .