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Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study

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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 β-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.

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Acknowledgments

The Ministry of Education, Science and Technological Development of Serbia support this work under Grant 172035. Authors gratefully acknowledge OpenEye Scientific Software, Santa Fe, NM, for the free academic licensing of software tools. The work reported makes use of results produced by the High-Performance Computing Infrastructure for South East Europe’s Research Communities (HP-SEE), a project co-funded by the European Commission (under Contract Number 261499) through the Seventh Framework Programme HP-SEE (http://www.hp-see.eu/). Authors gratefully acknowledge computational time provided on the PARADOX cluster at the Scientific Computing Laboratory of the Institute of Physics Belgrade (SCL-IPB), supported in part by the Serbian Ministry of Education, Science and Technological Development under projects No. ON171017 and III43007, and by the European Commission under FP7 projects PRACE-3IP and EGI-InSPIRE.

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Authors and Affiliations

  1. Innovation Center of the Faculty of Chemistry, University of Belgrade, Studentski Trg 12-16, Belgrade, Serbia

    Ilija N. Cvijetić

  2. Military - Technical Institute, Ratka Resanovića 1, Belgrade, Serbia

    Maja D. Vitorović-Todorović

  3. Department of Chemistry-IChTM, University of Belgrade, Njegoševa 12, Belgrade, Serbia

    Ivan O. Juranić & Branko J. Drakulić

  4. Faculty of Chemistry, University of Belgrade, Studentski Trg 12-16, Belgrade, Serbia

    Đura J. Nakarada & Milica D. Milosavljević

Authors
  1. Ilija N. Cvijetić
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  2. Maja D. Vitorović-Todorović
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  3. Ivan O. Juranić
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  4. Đura J. Nakarada
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  5. Milica D. Milosavljević
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  6. Branko J. Drakulić
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Corresponding authors

Correspondence to Ilija N. Cvijetić or Branko J. Drakulić.

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Cvijetić, I.N., Vitorović-Todorović, M.D., Juranić, I.O. et al. Reactivity of (E)-4-aryl-4-oxo-2-butenoic acid phenylamides with piperidine and benzylamine: kinetic and theoretical study. Monatsh Chem 145, 1297–1306 (2014). https://doi.org/10.1007/s00706-014-1223-8

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  • DOI: https://doi.org/10.1007/s00706-014-1223-8

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