Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships
Authors
Assaleh, Fathi H.
Marinković, Aleksandar

Nikolić, Jasmina

Prlainović, Nevena

Drmanić, Saša

Khan, Mohammad M.

Jovanović, Bratislav Ž.
Article (Published version)
Metadata
Show full item recordAbstract
Conformational stability of various 5-substituted orotic acid derivatives was studied by applying linear free energy relationships (LFER) to the C-13 NMR chemical shifts. The correlation analysis for the substituent-induced chemical shifts (SCS) with inductive (rI), and various resonance (rR) parameters were carried out through Single Substituent Parameter (SSP) and Dual Substituent Parameter (DSP) methods, and multiple regression analysis. Good Hammett correlations for all carbons were obtained, while electrophilic substituent constants better fitted for C2 carbon with electron-donor substituents. Conformational analysis of various derivatives using RB3LYP/6-311 ++G (3df,3dp) DFT method, together with C-13 NMR data suggests that most of the substituted orotic acid derivatives exist in planar conformation, except nitro and alkyl substituted derivatives. Internal rotation of carboxylic group showed significant impact on the extent of conjugative interaction making syn conformation more ...stable in all the derivatives studied. Further, of all 5-substituted orotic acid derivatives, diketo form proved to be the most stable form compared to zwitterionic and enol tautomeric forms. Optimized geometries and transmission effects of particular substituent through well-defined p-resonance units suggest that these units behave as isolated as well as conjugated fragments, depending on the type of substituent.
Keywords:
Conformational stability / 5-substituted orotic acids / Linear free energy relationships / C-13 NMR chemical shiftsSource:
Arabian Journal of Chemistry, 2019, 12, 8, 3357-3366Publisher:
- Elsevier, Amsterdam
Funding / projects:
- University of Zawia
- Study of the Synthesis, Structure and Activity of Natural and Synthetic Organic Compounds (RS-172013)
DOI: 10.1016/j.arabjc.2015.08.014
ISSN: 1878-5352
WoS: 000504900300158
Scopus: 2-s2.0-84964667746
Institution/Community
Tehnološko-metalurški fakultetTY - JOUR AU - Assaleh, Fathi H. AU - Marinković, Aleksandar AU - Nikolić, Jasmina AU - Prlainović, Nevena AU - Drmanić, Saša AU - Khan, Mohammad M. AU - Jovanović, Bratislav Ž. PY - 2019 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4115 AB - Conformational stability of various 5-substituted orotic acid derivatives was studied by applying linear free energy relationships (LFER) to the C-13 NMR chemical shifts. The correlation analysis for the substituent-induced chemical shifts (SCS) with inductive (rI), and various resonance (rR) parameters were carried out through Single Substituent Parameter (SSP) and Dual Substituent Parameter (DSP) methods, and multiple regression analysis. Good Hammett correlations for all carbons were obtained, while electrophilic substituent constants better fitted for C2 carbon with electron-donor substituents. Conformational analysis of various derivatives using RB3LYP/6-311 ++G (3df,3dp) DFT method, together with C-13 NMR data suggests that most of the substituted orotic acid derivatives exist in planar conformation, except nitro and alkyl substituted derivatives. Internal rotation of carboxylic group showed significant impact on the extent of conjugative interaction making syn conformation more stable in all the derivatives studied. Further, of all 5-substituted orotic acid derivatives, diketo form proved to be the most stable form compared to zwitterionic and enol tautomeric forms. Optimized geometries and transmission effects of particular substituent through well-defined p-resonance units suggest that these units behave as isolated as well as conjugated fragments, depending on the type of substituent. PB - Elsevier, Amsterdam T2 - Arabian Journal of Chemistry T1 - Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships EP - 3366 IS - 8 SP - 3357 VL - 12 DO - 10.1016/j.arabjc.2015.08.014 ER -
@article{ author = "Assaleh, Fathi H. and Marinković, Aleksandar and Nikolić, Jasmina and Prlainović, Nevena and Drmanić, Saša and Khan, Mohammad M. and Jovanović, Bratislav Ž.", year = "2019", abstract = "Conformational stability of various 5-substituted orotic acid derivatives was studied by applying linear free energy relationships (LFER) to the C-13 NMR chemical shifts. The correlation analysis for the substituent-induced chemical shifts (SCS) with inductive (rI), and various resonance (rR) parameters were carried out through Single Substituent Parameter (SSP) and Dual Substituent Parameter (DSP) methods, and multiple regression analysis. Good Hammett correlations for all carbons were obtained, while electrophilic substituent constants better fitted for C2 carbon with electron-donor substituents. Conformational analysis of various derivatives using RB3LYP/6-311 ++G (3df,3dp) DFT method, together with C-13 NMR data suggests that most of the substituted orotic acid derivatives exist in planar conformation, except nitro and alkyl substituted derivatives. Internal rotation of carboxylic group showed significant impact on the extent of conjugative interaction making syn conformation more stable in all the derivatives studied. Further, of all 5-substituted orotic acid derivatives, diketo form proved to be the most stable form compared to zwitterionic and enol tautomeric forms. Optimized geometries and transmission effects of particular substituent through well-defined p-resonance units suggest that these units behave as isolated as well as conjugated fragments, depending on the type of substituent.", publisher = "Elsevier, Amsterdam", journal = "Arabian Journal of Chemistry", title = "Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships", pages = "3366-3357", number = "8", volume = "12", doi = "10.1016/j.arabjc.2015.08.014" }
Assaleh, F. H., Marinković, A., Nikolić, J., Prlainović, N., Drmanić, S., Khan, M. M.,& Jovanović, B. Ž.. (2019). Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships. in Arabian Journal of Chemistry Elsevier, Amsterdam., 12(8), 3357-3366. https://doi.org/10.1016/j.arabjc.2015.08.014
Assaleh FH, Marinković A, Nikolić J, Prlainović N, Drmanić S, Khan MM, Jovanović BŽ. Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships. in Arabian Journal of Chemistry. 2019;12(8):3357-3366. doi:10.1016/j.arabjc.2015.08.014 .
Assaleh, Fathi H., Marinković, Aleksandar, Nikolić, Jasmina, Prlainović, Nevena, Drmanić, Saša, Khan, Mohammad M., Jovanović, Bratislav Ž., "Conformational stability of 5-substituted orotic acid derivatives analyzed by measuring C-13 NMR chemical shifts and applying linear free energy relationships" in Arabian Journal of Chemistry, 12, no. 8 (2019):3357-3366, https://doi.org/10.1016/j.arabjc.2015.08.014 . .