Reactivity and aromaticity of polyaromatics in radical cyclization reactions

被引：36

作者：

Van Speybroeck, V

Hemelsoet, K

Waroquier, M

Marin, GB

机构：

[1] Univ Ghent, Theoret Phys Lab, B-9000 Ghent, Belgium

[2] Univ Ghent, Petrochem Tech Lab, B-9000 Ghent, Belgium

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2004年 / 96卷 / 06期

关键词：

radical reactions; density functional calculations; kinetics; magnetic properties;

D O I：

10.1002/qua.10758

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Theoretical ab initio calculations are presented on cyclization. reactions of polyaromatics that occur by a radical mechanism. Such processes are one of the elementary steps for polyaromatic hydrocarbon formation in thermal cracking units and during soot formation. Ring closure can take place at various sites of the polyaromatic surface. It is the aim of this study to obtain insight into the influence of the local structure on the reactivity of the polyaromatics. Aromaticity is a determining factor for the reactivity and can be probed by various magnetic properties such as the diamagnetic susceptibilities, proton chemical shifts, and nucear-independent chemical shifts. A correlation is established between the magnetic properties and activation energy of the studied reactions. (C) 2003 Wiley Periodicals, Inc.

引用

收藏

页码：568 / 576

页数：9

相关论文

共 50 条

[11] Radical cyclization reactions with a zirconocene-olefin complex as an efficient single electron transfer reagent [J].

Fujita, K ;

Yorimitsu, H ;

Oshima, K .

SYNLETT, 2002, (02) :337-339

[12] Enantioselectivity and diastereoselectivity in reductive radical cyclization reactions of 3-(ω-iodoalkylidene)-piperidin-2-ones [J].

Dressel, Martina ;

Aechtner, Tobias ;

Bach, Thorsten .

SYNTHESIS-STUTTGART, 2006, (13) :2206-2214

[13] Photochemistry and Reactivity of the Phenyl Radical-Water System: A Matrix Isolation and Computational Study [J].

Mardyukov, Artur ;

Crespo-Otero, Rachel ;

Sanchez-Garcia, Elsa ;

Sander, Wolfram .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (29) :8679-8689

[14] Radical Cyclization of Trichloroacetamides: Synthesis of Lactams [J].

Coussanes, Guilhem ;

Vila, Xavier ;

Diaba, Faiza ;

Bonjoch, Josep .

SYNTHESIS-STUTTGART, 2017, 49 (07) :1481-1499

[15] Investigating the Reactivity of Radical Cations: Experimental and Computational Insights into the Reactions of Radical Cations with Alcohol and p-Toluene Sulfonamide Nucleophiles [J].

Campbell, John M. ;

Xu, Hai-Chao ;

Moeller, Kevin D. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (44) :18338-18344

[16] Reactivity-Structure-Based Rate Estimation Rules for Alkyl Radical H Atom Shift and Alkenyl Radical Cycloaddition Reactions [J].

Wang, Kun ;

Villano, Stephanie M. ;

Dean, Anthony M. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2015, 119 (28) :7205-7221

[17] The effect of solvation on the reactivity of 1,1-substituted ethylenes in hydroperoxyl radical addition reactions [J].

Pliss, Evgeny ;

Machtin, Viacheslav ;

Pliss, Roman ;

Sirik, Andrey ;

Loshadkin, Denis ;

Rusakov, Alexander .

REACTION KINETICS MECHANISMS AND CATALYSIS, 2018, 123 (02) :559-571

[18] Gas-Phase Kinetics of Hydroxyl Radical Reactions with Alkenes: Experiment and Theory [J].

Daranlot, Julien ;

Bergeat, Astrid ;

Caralp, Francoise ;

Caubet, Philippe ;

Costes, Michel ;

Forst, Wendell ;

Loison, Jean-Christophe ;

Hickson, Kevin M. .

CHEMPHYSCHEM, 2010, 11 (18) :4002-4010

[19] Radical addition reactions of phosphorus hydrides: Tuning the reactivity of phosphorus hydrides, the use of microwaves and Horner-Wadsworth-Emmons-type reactions [J].

Jessop, CM ;

Parsons, AF ;

Routledge, A ;

Irvine, DJ .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (06) :1547-1554

[20] Tandem radical reactions [J].

Albert, Matthias ;

Fensterbank, Louis ;

Lacote, Emmanuel ;

Malacria, Max .

RADICALS IN SYNTHESIS II: COMPLEX MOLECULES, 2006, 264 :1-62

← 1 2 3 4 5 →