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

[1] Long-range polar and steric effects in propionate-SG1-type alkoxyamines (SG1-CHMeCOOX): a multiparameter analysis [J].

Ananchenko, Gennady ;

Beaudoin, Emmanuel ;

Bertin, Denis ;

Gigmes, Didier ;

Lagarde, Pierre ;

Marque, Sylvain R. A. ;

Revalor, Eve ;

Tordo, Paul .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 2006, 19 (04) :269-275

[2] Chemically Triggered C-ON Bond Homolysis in Alkoxyamines. 6. Effect of the Counteranion [J].

Audran, Gerard ;

Bremond, Paul ;

Marque, Sylvain R. A. ;

Obame, Germain .

JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (15) :7754-7757

[3] Chemically Triggered C-ON Bond Homolysis of Alkoxyamines. 5. Cybotactic Effect [J].

Audran, Gerard ;

Bremond, Paul ;

Marque, Sylvain R. A. ;

Obame, Germain .

JOURNAL OF ORGANIC CHEMISTRY, 2012, 77 (21) :9634-9640

[4] Chemically triggered C-ON bond homolysis of alkoxyamines. Part 4: solvent effect [J].

Audran, Gerard ;

Bremond, Paul ;

Marque, Sylvain R. A. ;

Obame, Germain .

POLYMER CHEMISTRY, 2012, 3 (10) :2901-2908

[5] Can the first addition of alkyl radicals play a role in the fate of NMP? [J].

Bagryanskaya, Elena ;

Bertin, Denis ;

Gigmes, Didier ;

Kirilyuk, Igor ;

Marque, Sylvain R. A. ;

Reznikov, Vladimir ;

Roshchupkina, Galina ;

Zhurko, Irina ;

Zubenko, Dmitry .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 2008, 209 (13) :1345-1357

[6] Chemically Triggered C-ON Bond Homolysis in Alkoxyamines. Part 2: DFT Investigation and Application of the pH Effect on NMP [J].

Bagryanskaya, Elena ;

Bremond, Paul ;

Edeleva, Mariya ;

Marque, Sylvain R. A. ;

Parkhomenko, Dmitriy ;

Roubaud, Valerie ;

Siri, Didier .

MACROMOLECULAR RAPID COMMUNICATIONS, 2012, 33 (02) :152-157

[7] Alkoxyamine C-ON bond homolysis: Stereoelectronic effects [J].

Beaudoin, E ;

Bertin, D ;

Gigmes, D ;

Marque, SRA ;

Siri, D ;

Tordo, P .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (07) :1755-1768

[8] Long-range polar effect on the C-ON bond homolysis in (tert-butyl[1-(diethylphosphonyl)-2,2-dimethylpropyl]-aminoxyl) SG1-based alkoxyamines [J].

Bertin, D ;

Gigmes, D ;

Marque, SRA ;

Milardo, S ;

Peri, J ;

Tordo, P .

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 2004, 69 (12) :2223-2238

[9] Polar, steric, and stabilization effects in alkoxyamines C-ON bond homolysis: A multiparameter analysis [J].

Bertin, D ;

Gigmes, D ;

Marque, SRA ;

Tordo, P .

MACROMOLECULES, 2005, 38 (07) :2638-2650

[10] Synthesis of a series of SG1 2-[N-tert-butyl-N(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxyl] Based alkoxyamines, SG1-CH(Me)CO2R, and measurement of the homolysis rate constants of the C-ON bond [J].

Bertin, D ;

Gigmes, D ;

Marque, S ;

Maurin, R ;

Tordo, P .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2004, 42 (14) :3504-3515

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