Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study
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2014
Authors
Cvijetić, IlijaVitorović-Todorović, Maja D.
Juranić, Ivan O.
Nakarada, Dura J.
Milosavljević, Milica D.
Drakulić, Branko J.
Article (Published version)
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Rates of the aza-Michael addition of piperidine and benzylamine to thirteen (E)-4-aryl-4-oxo-2-butenoic acid phenylamides (AACPs) are reported. Progress of the reaction was monitored by UV/Vis spectroscopy. The 2D NMR spectra confirmed regioselectivity of the reactions. Piperidine and benzylamine provide exclusively beta-adducts in respect to the aroyl keto group. Influence of the substituents of the aroyl phenyl ring of AACPs on the rate of the reaction was quantified by Hammett substituent constants, partial atomic charges, and the energies of frontier orbitals. Good correlations between second-order rate constants and the Hammett substituent constants were obtained (r = 0.98, piperidine; r = 0.94, benzylamine) for para-, and meta-, para-substituted derivatives. Best correlations were obtained with the energies of the lowest unoccupied molecular orbitals of compounds, derived from the MP2 level of theory. Calculated UV/Vis spectra of representative AACPs and their Michael adduct with... piperidine and benzylamine are in fair agreement with experimentally obtained data.
Keywords:
Michael addition / UV/Vis spectroscopy / Kinetics / Linear free-energy relationships / ZINDO/S calculationsSource:
Monatshefte Fur Chemie, 2014, 145, 8, 1297-1306Publisher:
- Springer Wien, Wien
Funding / projects:
- Modeling and Numerical Simulations of Complex Many-Body Systems (RS-MESTD-Basic Research (BR or ON)-171017)
- 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)
- Studying climate change and its influence on environment: impacts, adaptation and mitigation (RS-MESTD-Integrated and Interdisciplinary Research (IIR or III)-43007)
- High-Performance Computing Infrastructure for South East Europe's Research Communities (EU-FP7-261499)
DOI: 10.1007/s00706-014-1223-8
ISSN: 0026-9247
WoS: 000339378800010
Scopus: 2-s2.0-84904268026
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Institution/Community
Inovacioni centar / Innovation CentreTY - JOUR AU - Cvijetić, Ilija AU - Vitorović-Todorović, Maja D. AU - Juranić, Ivan O. AU - Nakarada, Dura J. AU - Milosavljević, Milica D. AU - Drakulić, Branko J. PY - 2014 UR - https://cherry.chem.bg.ac.rs/handle/123456789/1816 AB - Rates of the aza-Michael addition of piperidine and benzylamine to thirteen (E)-4-aryl-4-oxo-2-butenoic acid phenylamides (AACPs) are reported. Progress of the reaction was monitored by UV/Vis spectroscopy. The 2D NMR spectra confirmed regioselectivity of the reactions. Piperidine and benzylamine provide exclusively beta-adducts in respect to the aroyl keto group. Influence of the substituents of the aroyl phenyl ring of AACPs on the rate of the reaction was quantified by Hammett substituent constants, partial atomic charges, and the energies of frontier orbitals. Good correlations between second-order rate constants and the Hammett substituent constants were obtained (r = 0.98, piperidine; r = 0.94, benzylamine) for para-, and meta-, para-substituted derivatives. Best correlations were obtained with the energies of the lowest unoccupied molecular orbitals of compounds, derived from the MP2 level of theory. Calculated UV/Vis spectra of representative AACPs and their Michael adduct with piperidine and benzylamine are in fair agreement with experimentally obtained data. PB - Springer Wien, Wien T2 - Monatshefte Fur Chemie T1 - Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study VL - 145 IS - 8 SP - 1297 EP - 1306 DO - 10.1007/s00706-014-1223-8 ER -
@article{ author = "Cvijetić, Ilija and Vitorović-Todorović, Maja D. and Juranić, Ivan O. and Nakarada, Dura J. and Milosavljević, Milica D. and Drakulić, Branko J.", year = "2014", abstract = "Rates of the aza-Michael addition of piperidine and benzylamine to thirteen (E)-4-aryl-4-oxo-2-butenoic acid phenylamides (AACPs) are reported. Progress of the reaction was monitored by UV/Vis spectroscopy. The 2D NMR spectra confirmed regioselectivity of the reactions. Piperidine and benzylamine provide exclusively beta-adducts in respect to the aroyl keto group. Influence of the substituents of the aroyl phenyl ring of AACPs on the rate of the reaction was quantified by Hammett substituent constants, partial atomic charges, and the energies of frontier orbitals. Good correlations between second-order rate constants and the Hammett substituent constants were obtained (r = 0.98, piperidine; r = 0.94, benzylamine) for para-, and meta-, para-substituted derivatives. Best correlations were obtained with the energies of the lowest unoccupied molecular orbitals of compounds, derived from the MP2 level of theory. Calculated UV/Vis spectra of representative AACPs and their Michael adduct with piperidine and benzylamine are in fair agreement with experimentally obtained data.", publisher = "Springer Wien, Wien", journal = "Monatshefte Fur Chemie", title = "Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study", volume = "145", number = "8", pages = "1297-1306", doi = "10.1007/s00706-014-1223-8" }
Cvijetić, I., Vitorović-Todorović, M. D., Juranić, I. O., Nakarada, D. J., Milosavljević, M. D.,& Drakulić, B. J.. (2014). Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study. in Monatshefte Fur Chemie Springer Wien, Wien., 145(8), 1297-1306. https://doi.org/10.1007/s00706-014-1223-8
Cvijetić I, Vitorović-Todorović MD, Juranić IO, Nakarada DJ, Milosavljević MD, Drakulić BJ. Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study. in Monatshefte Fur Chemie. 2014;145(8):1297-1306. doi:10.1007/s00706-014-1223-8 .
Cvijetić, Ilija, Vitorović-Todorović, Maja D., Juranić, Ivan O., Nakarada, Dura J., Milosavljević, Milica D., Drakulić, Branko J., "Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study" in Monatshefte Fur Chemie, 145, no. 8 (2014):1297-1306, https://doi.org/10.1007/s00706-014-1223-8 . .