NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines

Sergey Cherkasov, Dmitriy Parkhomenko, Alexander Genaev, Georgii Salnikov, Mariya Edeleva, Denis Morozov, Tatyana Rybalova, Igor Kirilyuk, Sylvain R.A. Marque, Elena Bagryanskaya

Результат исследования: Научные публикации в периодических изданияхстатьярецензирование

Аннотация

Three alkoxyamines based on imidazoline radicals with a pyridine functional group-potential initiators of nitroxide-mediated, controlled radical polymerization-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 β-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.

Язык оригиналаанглийский
ЖурналMolecules (Basel, Switzerland)
Том25
Номер выпуска21
DOI
СостояниеОпубликовано - 1 ноя 2020

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