Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study
Abstract
The reactivity of fifteen (E)-4-aryl-4-oxo-2-butenoic (aroylacrylic) acid arylamides toward thiols was studied, measuring the rate constants of the addition of model thiol nucleophile, 2-mercaptoethanol. The influence of the variation of the substituents on the phenyl rings on the rate of reaction was quantified using the Hammett substituent constants and descriptors derived from ab initio or semiempirical calculations (atomic charges, HOMO, and LUMO). Statistically significant linear correlations between second-order rate constants and Hammett substituent constants, as well as energies of LUMO orbitals, were obtained. Substituents on both aroyl and arylamido moieties were shown to influence the reactivity of studied compounds toward thiols. The regioselectivity of reaction was confirmed by NMR spectroscopy. Exclusively beta-addition product with respect to the aroyl keto group was obtained. The determined enthalpy and entropy of activation were found to be in agreement with the propos...ed reaction mechanism, which includes a highly ordered transition state.
Keywords:
Thia-Michael addition / Aroylacrylic acid phenylamides / Kinetics / Quantum chemical calculations / NMR spectroscopySource:
Monatshefte Fur Chemie, 2013, 144, 12, 1815-1824Publisher:
- Springer Wien, Wien
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-MESTD-Basic Research (BR or ON)-172035)
- High-Performance Computing Infrastructure for South East Europe's Research Communities (EU-FP7-261499)
DOI: 10.1007/s00706-013-1084-6
ISSN: 0026-9247
WoS: 000327083100009
Scopus: 2-s2.0-84961983959
Collections
Institution/Community
IHTMTY - JOUR AU - Cvijetić, Ilija AU - Vitorović-Todorović, Maja D. AU - Juranić, Ivan AU - Drakulić, Branko PY - 2013 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/2689 AB - The reactivity of fifteen (E)-4-aryl-4-oxo-2-butenoic (aroylacrylic) acid arylamides toward thiols was studied, measuring the rate constants of the addition of model thiol nucleophile, 2-mercaptoethanol. The influence of the variation of the substituents on the phenyl rings on the rate of reaction was quantified using the Hammett substituent constants and descriptors derived from ab initio or semiempirical calculations (atomic charges, HOMO, and LUMO). Statistically significant linear correlations between second-order rate constants and Hammett substituent constants, as well as energies of LUMO orbitals, were obtained. Substituents on both aroyl and arylamido moieties were shown to influence the reactivity of studied compounds toward thiols. The regioselectivity of reaction was confirmed by NMR spectroscopy. Exclusively beta-addition product with respect to the aroyl keto group was obtained. The determined enthalpy and entropy of activation were found to be in agreement with the proposed reaction mechanism, which includes a highly ordered transition state. PB - Springer Wien, Wien T2 - Monatshefte Fur Chemie T1 - Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study VL - 144 IS - 12 SP - 1815 EP - 1824 DO - 10.1007/s00706-013-1084-6 ER -
@article{ author = "Cvijetić, Ilija and Vitorović-Todorović, Maja D. and Juranić, Ivan and Drakulić, Branko", year = "2013", abstract = "The reactivity of fifteen (E)-4-aryl-4-oxo-2-butenoic (aroylacrylic) acid arylamides toward thiols was studied, measuring the rate constants of the addition of model thiol nucleophile, 2-mercaptoethanol. The influence of the variation of the substituents on the phenyl rings on the rate of reaction was quantified using the Hammett substituent constants and descriptors derived from ab initio or semiempirical calculations (atomic charges, HOMO, and LUMO). Statistically significant linear correlations between second-order rate constants and Hammett substituent constants, as well as energies of LUMO orbitals, were obtained. Substituents on both aroyl and arylamido moieties were shown to influence the reactivity of studied compounds toward thiols. The regioselectivity of reaction was confirmed by NMR spectroscopy. Exclusively beta-addition product with respect to the aroyl keto group was obtained. The determined enthalpy and entropy of activation were found to be in agreement with the proposed reaction mechanism, which includes a highly ordered transition state.", publisher = "Springer Wien, Wien", journal = "Monatshefte Fur Chemie", title = "Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study", volume = "144", number = "12", pages = "1815-1824", doi = "10.1007/s00706-013-1084-6" }
Cvijetić, I., Vitorović-Todorović, M. D., Juranić, I.,& Drakulić, B.. (2013). Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study. in Monatshefte Fur Chemie Springer Wien, Wien., 144(12), 1815-1824. https://doi.org/10.1007/s00706-013-1084-6
Cvijetić I, Vitorović-Todorović MD, Juranić I, Drakulić B. Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study. in Monatshefte Fur Chemie. 2013;144(12):1815-1824. doi:10.1007/s00706-013-1084-6 .
Cvijetić, Ilija, Vitorović-Todorović, Maja D., Juranić, Ivan, Drakulić, Branko, "Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid arylamides toward 2-mercaptoethanol. A LFER study" in Monatshefte Fur Chemie, 144, no. 12 (2013):1815-1824, https://doi.org/10.1007/s00706-013-1084-6 . .