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NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines.

ABSTRACT: 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 ?-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.

SUBMITTER: Cherkasov S

PROVIDER: S-EPMC7663419 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines.

Cherkasov Sergey S Parkhomenko Dmitriy D Genaev Alexander A Salnikov Georgii G Edeleva Mariya M Morozov Denis D Rybalova Tatyana T Kirilyuk Igor I Marque Sylvain R A SRA Bagryanskaya Elena E

Molecules (Basel, Switzerland) 20201101 21

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 t ...[more]

PMID: 33139669

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