NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines
| Autor: | Tatyana V. Rybalova, Denis A. Morozov, Elena G. Bagryanskaya, Dmitriy Parkhomenko, Sylvain R. A. Marque, Alexander M. Genaev, Sergey A. Cherkasov, Igor A. Kirilyuk, Georgii E. Salnikov, Mariya V. Edeleva |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
homolysis
Nitroxide mediated radical polymerization Radical Kinetics Pharmaceutical Science chirality Photochemistry stereoisomerization Article Analytical Chemistry law.invention lcsh:QD241-441 Cyclic N-Oxides chemistry.chemical_compound Reaction rate constant lcsh:Organic chemistry law Drug Discovery Pyridine nitroxide mediated polymerization Physical and Theoretical Chemistry Amines Electron paramagnetic resonance scavenger Nuclear Magnetic Resonance Biomolecular imidazoline radical nitrogen inversion Molecular Structure Thiophenol Organic Chemistry Electron Spin Resonance Spectroscopy Homolysis chemistry Chemistry (miscellaneous) Molecular Medicine nitroxide alkoxyamine |
| Zdroj: | Molecules Molecules, Vol 25, Iss 5080, p 5080 (2020) Volume 25 Issue 21 |
| ISSN: | 1420-3049 |
| Popis: | Three alkoxyamines based on imidazoline radicals with a pyridine functional group&mdash potential initiators of nitroxide-mediated, controlled radical polymerization&mdash were synthesized. Electron Paramagnetic Resonance (EPR) measurements reveal biexponential kinetics for the thermolysis for diastereomeric alkoxyamines and monoexponential kinetics for an achiral alkoxyamine. For comparison, the thermolysis of all three alkoxyamines was studied by NMR in the presence of three different scavengers, namely tetramethylpiperidine-N-oxyl (TEMPO), thiophenol (PhSH), and &beta mercaptoethanol (BME), and detailed analysis of products was performed. NMR differentiates between N-inversion, epimerization, and homolysis reactions. The choice of scavenger is crucial for making a reliable and accurate estimate of the true homolysis rate constant. |
| Databáze: | OpenAIRE |
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