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C-ON bond homolysis in alkoxyamines. Part 12: the effect of the para-substituent in the 1-phenylethyl fragment

Gérard Audran 1 Paul Brémond 1 Jean-Patrick Joly 1 Marque S.R.A. 2, 1 Toshihide Yamasaki 1
1 ICR - Institut de Chimie Radicalaire
2 RAS, SB, NN Vorozhtsov Novosibirsk Inst Organ Chem,
Abstract : The application of alkoxyamines as initiators/controllers in nitroxide mediated polymerization and as agents for theranostics requires the development of switchable (from stable one to labile one) alkoxyamines. One way to achieve this is to tune the polarity of various groups carried by either the alkyl fragment or the nitroxyl fragment. Thus, the effect of protonation/deprotonation of the para-functionalized aryl moiety carried by the alkyl fragment in diethyl(2,2-dimethyl-1-((1,1-dimethylethyl)(1-para-subsituted-phenylethoxy) amino) propyl) phosphonate is investigated. An increase in k(d) is observed with increasing localized electrical effect, i.e., in the presence of electron withdrawing groups at the para position of the phenyl ring. A striking effect of the intimate ion pair on kd is also observed.
Keywords : RADICAL STABILIZATION ENERGIES METHYLENECYCLOPROPANE REARRANGEMENT SG1-BASED ALKOXYAMINES SPIN-DELOCALIZATION BENZYL RADICALS POLYMERIZATION NITROXIDE CONSTANTS POLAR VALUES
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https://hal-amu.archives-ouvertes.fr/hal-01408206
Contributor : Valerie Roubaud <>
Submitted on : Saturday, December 3, 2016 - 4:32:05 PM
Last modification on : Thursday, January 18, 2018 - 1:49:43 AM

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Gérard Audran, Paul Brémond, Jean-Patrick Joly, Marque S.R.A., Toshihide Yamasaki. C-ON bond homolysis in alkoxyamines. Part 12: the effect of the para-substituent in the 1-phenylethyl fragment. Organic and Biomolecular Chemistry, Royal Society of Chemistry, 2016, 14 (14), pp.3574-3583. ⟨10.1039/c6ob00384b⟩. ⟨hal-01408206⟩

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