Chemically triggered C-ON bond homolysis in alkoxyamines. Part 7. Remote polar effect

被引：6

作者：

Audran, Gerard ^{[1
]}

Ibanou, Matisse Bim Batsiandzy ^{[1
]}

Bremond, Paul ^{[1
]}

Marque, Sylvain R. A. ^{[1
]}

Obame, Germain ^{[1
]}

Roubaud, Valerie ^{[1
]}

Siri, Didier ^{[1
]}

机构：

[1] Univ Aix Marseille, CNRS, UMR 7273, ICR, F-13397 Marseille 20, France

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2014年 / 27卷 / 05期

关键词：

alkoxyamines; remote polar effect; homolysis; kinetics; radical initiators; NITROXIDE-MEDIATED POLYMERIZATION; FREE-RADICAL POLYMERIZATION; LONG-RANGE POLAR; INITIATING ALKOXYAMINE; CONSTANTS;

D O I：

10.1002/poc.3275

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In a recent work (Org. Lett. 2012, 14, 358-361), we showed that the activation by benzylation of alkoxyamine 1 (diethyl (1-(tert-butyl(1-(pyridin-4-yl)ethoxy)amino)-2,2-dimethylpropyl)phosphonate) afforded a surprisingly large C-ON bond homolysis rate constant k(d). Taking advantage of the easy preparation of para-X-benzyl-activated alkoxyamines 2 and of the presence of a shielding methylene group between the two aromatic moieties, we investigated the long range (10 bonds between the X group and the C-ON bond) polar effect for X=H, F, OMe, CN, NO2, NMe2, +NHMe2,Br-. It was observed that the effect was weak (4-fold) and mainly due to the zwiterionic mesomeric forms generated by the presence of group X on the para position, i.e. k(d) increased for CN and NO2 and decreased for OMe, NMe2 and +NMe2H,Br-. DFT calculations at the B3LYP/6-31G(d,p) level were performed to determine orbital interactions (natural bond orbital (NBO) analysis), Mulliken and NBO charges which support the reactivity described. Copyright (c) 2014 John Wiley & Sons, Ltd.

引用

页码：387 / 391

页数：5

共 38 条

[31]

MOAD G, 2006, CHEM RADICAL POLYM 2

[32] N-alkoxyamines: Synthesis, properties, and applications in polymer chemistry, organic synthesis, and materials science [J].

Nesvadba, Peter .

CHIMIA, 2006, 60 (12) :832-840

[33] Nitroxide-mediated polymerization [J].

Nicolas, Julien ;

Guillaneuf, Yohann ;

Lefay, Catherine ;

Bertin, Denis ;

Gigmes, Didier ;

Charleux, Bernadette .

PROGRESS IN POLYMER SCIENCE, 2013, 38 (01) :63-235

[34]

Rizzardo E., 1986, US patent, Patent No. [4581429, US4581429A]

[35]

Solomon D. H., 1985, EP Pat, Patent No. 135280

[36]

Solomon D. H., 1985, CHEM ABSTR, V102

[37] Nitroxides: Applications in Synthesis and in Polymer Chemistry [J].

Tebben, Ludger ;

Studer, Armido .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (22) :5034-5068

[38] Role of the alkyl fragment of initiating alkoxyamine in nitroxide mediated polymerization of styrene [J].

Zubenko, D. P. ;

Kirilyuk, I. A. ;

Marque, S. ;

Chuikov, I. P. ;

Bagryanskaya, E. G. .

POLYMER SCIENCE SERIES B, 2010, 52 (5-6) :327-338

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