NMR and EPR Study of Homolysis of Diastereomeric Alkoxyamines

被引：4

作者：

Cherkasov, Sergey ^{[1
,2
]}

Parkhomenko, Dmitriy ^{[1
]}

Genaev, Alexander ^{[1
]}

Salnikov, Georgii ^{[1
]}

Edeleva, Mariya ^{[1
]}

Morozov, Denis ^{[1
]}

Rybalova, Tatyana ^{[1
]}

Kirilyuk, Igor ^{[1
]}

Marque, Sylvain R. A. ^{[3
]}

Bagryanskaya, Elena ^{[1
]}

机构：

[1] NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Pr Lavrentjeva 9, Novosibirsk 630090, Russia

[2] Natl Res Univ, Novosibirsk State Univ, Novosibirsk 630090, Russia

[3] Aix Marseille Univ, ICR, CNRS, UMR 7273, Case 551,Ave Escadrille Normandie Niemen, F-13397 Marseille 20, France

来源：

MOLECULES | 2020年 / 25卷 / 21期

关键词：

nitroxide; alkoxyamine; nitroxide mediated polymerization; kinetics; scavenger; imidazoline radical; homolysis; nitrogen inversion; chirality; stereoisomerization; C-ON BOND; RADICAL POLYMERIZATION; MODEL ALKOXYAMINES; CONTROL AGENTS; N-O; NITROXIDES; IMIDAZOLINE; SYSTEMS; DECOMPOSITION; LIMITATIONS;

D O I：

10.3390/molecules25215080

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

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 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.

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页数：20

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