A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane
Само за регистроване кориснике
2016
Аутори
Assaleh, Fathi H.Marinković, Aleksandar
Nikolić, Jasmina
Drmanić, Saša
Brković, Danijela V
Prlainović, Nevena
Jovanović, Bratislav Ž.
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Linear free energy relationships (LFER) were applied to the kinetic data for the reaction of 5-substituted orotic acids, series 1, with diazodiphenylmethane (DDM) in N,N-dimethylformamide and compared with results obtained for 2-substituted benzoic acids, series 2. The correlation analysis of the kinetic data with sigma substituent parameters was carried out using SSP (single substituent parameter) methods. From the sign and value of proportinality constant rho, lower sensitivity to the substituent effect was obtained in series 1, 0.876, than in the series 2, 1.877. Evaluation of substituent "ortho-effect" was performed using the Charton model, which includes the steric substituent parameter, and Fujita and Nishioka's model, which describes the total ortho-effect as contribution of ordinary polar effect, the ortho-steric and ortho-polar effects. Results of correlations, obtained by using the Charton model, showed highest contribution of the polar effect, 0.861 vs. 2.101, whereas the st...eric effect is of lowest significance, 0.117 vs. 0.055, for series 1 and 2, respectively. Also, a low negative value of coefficient with the steric effect, -0.08, obtained from the Fujita-Nishioka model indicated low steric effect, influencing a decrease of the reaction rate in series 1. The structural and substituent effects were also studied by using the density functional theory method, and together with kinetic data, it gave a better insight into the influence of the effect of both geometry and substituent on the pi-electron density shift induced reactivity of investigated acids. geometry and substituent on the pi-electron density shift induced reactivity of investigated acids.
Извор:
International Journal of Chemical Kinetics, 2016, 48, 7, 367-378Издавач:
- Wiley, Hoboken
Финансирање / пројекти:
- Ministry of Education, Science and Environmental Protection, Republic of Serbia
- Проучавање синтезе, структуре и активности органских једињења природног и синтетског порекла (RS-MESTD-Basic Research (BR or ON)-172013)
DOI: 10.1002/kin.20997
ISSN: 0538-8066
WoS: 000375084700003
Scopus: 2-s2.0-84964661432
Институција/група
Tehnološko-metalurški fakultetTY - JOUR AU - Assaleh, Fathi H. AU - Marinković, Aleksandar AU - Nikolić, Jasmina AU - Drmanić, Saša AU - Brković, Danijela V AU - Prlainović, Nevena AU - Jovanović, Bratislav Ž. PY - 2016 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/3265 AB - Linear free energy relationships (LFER) were applied to the kinetic data for the reaction of 5-substituted orotic acids, series 1, with diazodiphenylmethane (DDM) in N,N-dimethylformamide and compared with results obtained for 2-substituted benzoic acids, series 2. The correlation analysis of the kinetic data with sigma substituent parameters was carried out using SSP (single substituent parameter) methods. From the sign and value of proportinality constant rho, lower sensitivity to the substituent effect was obtained in series 1, 0.876, than in the series 2, 1.877. Evaluation of substituent "ortho-effect" was performed using the Charton model, which includes the steric substituent parameter, and Fujita and Nishioka's model, which describes the total ortho-effect as contribution of ordinary polar effect, the ortho-steric and ortho-polar effects. Results of correlations, obtained by using the Charton model, showed highest contribution of the polar effect, 0.861 vs. 2.101, whereas the steric effect is of lowest significance, 0.117 vs. 0.055, for series 1 and 2, respectively. Also, a low negative value of coefficient with the steric effect, -0.08, obtained from the Fujita-Nishioka model indicated low steric effect, influencing a decrease of the reaction rate in series 1. The structural and substituent effects were also studied by using the density functional theory method, and together with kinetic data, it gave a better insight into the influence of the effect of both geometry and substituent on the pi-electron density shift induced reactivity of investigated acids. geometry and substituent on the pi-electron density shift induced reactivity of investigated acids. PB - Wiley, Hoboken T2 - International Journal of Chemical Kinetics T1 - A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane EP - 378 IS - 7 SP - 367 VL - 48 DO - 10.1002/kin.20997 ER -
@article{ author = "Assaleh, Fathi H. and Marinković, Aleksandar and Nikolić, Jasmina and Drmanić, Saša and Brković, Danijela V and Prlainović, Nevena and Jovanović, Bratislav Ž.", year = "2016", abstract = "Linear free energy relationships (LFER) were applied to the kinetic data for the reaction of 5-substituted orotic acids, series 1, with diazodiphenylmethane (DDM) in N,N-dimethylformamide and compared with results obtained for 2-substituted benzoic acids, series 2. The correlation analysis of the kinetic data with sigma substituent parameters was carried out using SSP (single substituent parameter) methods. From the sign and value of proportinality constant rho, lower sensitivity to the substituent effect was obtained in series 1, 0.876, than in the series 2, 1.877. Evaluation of substituent "ortho-effect" was performed using the Charton model, which includes the steric substituent parameter, and Fujita and Nishioka's model, which describes the total ortho-effect as contribution of ordinary polar effect, the ortho-steric and ortho-polar effects. Results of correlations, obtained by using the Charton model, showed highest contribution of the polar effect, 0.861 vs. 2.101, whereas the steric effect is of lowest significance, 0.117 vs. 0.055, for series 1 and 2, respectively. Also, a low negative value of coefficient with the steric effect, -0.08, obtained from the Fujita-Nishioka model indicated low steric effect, influencing a decrease of the reaction rate in series 1. The structural and substituent effects were also studied by using the density functional theory method, and together with kinetic data, it gave a better insight into the influence of the effect of both geometry and substituent on the pi-electron density shift induced reactivity of investigated acids. geometry and substituent on the pi-electron density shift induced reactivity of investigated acids.", publisher = "Wiley, Hoboken", journal = "International Journal of Chemical Kinetics", title = "A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane", pages = "378-367", number = "7", volume = "48", doi = "10.1002/kin.20997" }
Assaleh, F. H., Marinković, A., Nikolić, J., Drmanić, S., Brković, D. V., Prlainović, N.,& Jovanović, B. Ž.. (2016). A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane. in International Journal of Chemical Kinetics Wiley, Hoboken., 48(7), 367-378. https://doi.org/10.1002/kin.20997
Assaleh FH, Marinković A, Nikolić J, Drmanić S, Brković DV, Prlainović N, Jovanović BŽ. A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane. in International Journal of Chemical Kinetics. 2016;48(7):367-378. doi:10.1002/kin.20997 .
Assaleh, Fathi H., Marinković, Aleksandar, Nikolić, Jasmina, Drmanić, Saša, Brković, Danijela V, Prlainović, Nevena, Jovanović, Bratislav Ž., "A LFER Kinetic Study of The Reaction of 5-Substituted Orotic Acids with Diazodiphenylmethane" in International Journal of Chemical Kinetics, 48, no. 7 (2016):367-378, https://doi.org/10.1002/kin.20997 . .