Audran Gérard, Bagryanskaya Elena G, Brémond Paul, Edeleva Mariya V, Marque Sylvain R A, Parkhomenko Dmitriy A, Rogozhnikova Olga Yu, Tormyshev Victor M, Tretyakov Evgeny V, Trukhin Dmitry V, Zhivetyeva Svetlana I
Aix-Marseille Univ, CNRS, ICR, UMR 7273, case 551, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20 France.
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS. 9, Lavrentjev Ave, Novosibirsk 630090, Russia.
Polym Chem. 2016 Nov 14;7(42):6490-6499. doi: 10.1039/C6PY01303A. Epub 2016 Oct 12.
Recently, new applications of trityl-nitroxide biradicals were proposed. In the present study, attachment of a trityl radical to alkoxyamines was performed for the first time. The rate constants of C-ON bond homolysis in these alkoxyamines were measured and found to be equal to those for alkoxyamines without trityl. The electron paramagnetic resonance (EPR) spectra of the products of alkoxyamine homolysis (trityl-TEMPO and trityl-SG1 biradicals) were recorded, and the corresponding exchange interactions were estimated. The decomposition of trityl-alkoxyamine showed more than an 80% yield of biradicals, meaning that the C-ON bond homolysis is the main reaction. The suitability of these labelled initiators/controllers for polymerisation was exemplified by means of successful nitroxide-mediated polymerisation (NMP) of styrene. Thus, this is the first report of a spin-labelled alkoxyamine suitable for NMP.
最近，提出了三苯甲基-氮氧化物双自由基的新应用。在本研究中，首次将三苯甲基自由基连接到烷氧基胺上。测量了这些烷氧基胺中C-ON键均裂的速率常数，发现其与没有三苯甲基的烷氧基胺的速率常数相等。记录了烷氧基胺均裂产物（三苯甲基-TEMPO和三苯甲基-SG1双自由基）的电子顺磁共振（EPR）光谱，并估计了相应的交换相互作用。三苯甲基-烷氧基胺的分解显示双自由基的产率超过80%，这意味着C-ON键均裂是主要反应。通过苯乙烯的成功氮氧自由基介导聚合（NMP）举例说明了这些标记的引发剂/控制剂对聚合的适用性。因此，这是关于适用于NMP的自旋标记烷氧基胺的首次报道。
