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Hydrogen-Bonding Effects for the C-ON Bond Homolysis and Reformation Reactions of Alkoxyamines Full article

Journal Macromolecular Chemistry and Physics
ISSN: 1022-1352 , E-ISSN: 1521-3935
Output data Year: 2015, Volume: 216, Number: 5, Pages: 475-488 Pages count : DOI: 10.1002/macp.201400438
Tags alkoxyamines; intramolecular hydrogen bond; kinetics; solvent effects
Authors Bagryanskaya Elena G. 1,2,3 , Bremond Paul 4 , Butscher Teddy 4 , Marque Sylvain R. A. 4 , Parkhomenko Dmitry 1,3 , Roubaud Valerie 4 , Siri Didier 4 , Viel Stephane 4
Affiliations
1 (Данные Web of science) Int Tomog Ctr SB RAS, Novosibirsk 630090, Russia
2 (Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Novosibirsk 630090, Russia
3 (Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
4 (Данные Web of science) Aix Marseille Univ, CNRS, ICR UMR 7273, F-13397 Marseille 20, France

Abstract: N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-O-(2-carboxyprop-2-yl) hydroxylamine (BlocBuilder MA) is, among the commercially available alkoxyamines, one of the most efficient for nitroxide-mediated polymerization (NMP). However, recent results have shown that it does not perform well for the NMP of isoprene. The occurrence of intramolecular hydrogen bonding (IHB) between the carboxylic function and the diethoxyphosphoryl group has been proposed as the reason for its low efficiency. In this article, the presence of this IHB is confirmed using IR, P-31 NMR, P-31-H-1 HOESY, and DFT calculation results. The solvent effect on this IHB and consequently on k(d) values is also investigated. However, combining kinetic analysis and rate measurements in various solvents, the influence of this IHB on the C-ON bond homolysis and reformation in alkoxyamine is shown to be very weak.
Cite: Bagryanskaya E.G. , Bremond P. , Butscher T. , Marque S.R.A. , Parkhomenko D. , Roubaud V. , Siri D. , Viel S.
Hydrogen-Bonding Effects for the C-ON Bond Homolysis and Reformation Reactions of Alkoxyamines
Macromolecular Chemistry and Physics. 2015. V.216. N5. P.475-488. DOI: 10.1002/macp.201400438 WOS Scopus РИНЦ
Dates:
Published online: Dec 22, 2014
Published print: Mar 1, 2015
Identifiers:
Web of science WOS:000350507500001
Scopus 2-s2.0-84925002612
Elibrary 24018272
OpenAlex W2104852390
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