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	Formation of nitroxide radicals from secondary amines and peracids: A peroxyl radical oxidation pathway derived from electron spin resonance detection and density functional theory calculation
	Shi, Hong-Chang ; Li, Yong
	2010-05-06 ; 2010-05-06
关键词	secondary amine peroxyl radical nitroxide radical ESR detection DFT calculation META-CHLOROPERBENZOIC ACID MOLECULE-INDUCED HOMOLYSIS OXENOID OXYGEN INSERTION HYDROGEN PEROXIDE OLEFIN EPOXIDATION COMPUTATIONAL DFT ALCOHOLS MECHANISM ALKENES LABELS Chemistry, Physical
中文摘要	By electron spin resonance (ESR) detection and quantum chemical calculation based on the density functional theory (DFT) at the B3LYP/63 1 G(d) level, we found that the formation of nitroxide radicals from secondary amines and peracids is a peroxyl radical oxidation reaction, where peroxyl radicals are the reactive intermediates of peracids in the oxidation. The DFT calculation revealed the transition structures and activation barriers of oxidizing pyrrolidine by the peroxyl radicals of peracetic acid and percarboximidic acid. Their barriers are 11.75 and 12.35 kcal/mol, respectively, showing that the peroxyl radicals have high reactivity on secondary amines. A reaction path calculation (IRC) of the oxidation of pyrrolidine by the peroxyl radical of percarboximidic acid illustrated the process of the formation of nitroxide radical: firstly, the terminal oxygen atom of the peroxyl radical R-O-O center dot attacks the nitrogen atom of secondary amine and forms a N-O bond, and then the hydrogen atom from the N-H of the secondary amine is transferred to the imido nitrogen atom or the carbonyl oxygen atom of peracid and finally forms a new N-H or O-H bond. (C) 2007 Elsevier B.V. All rights reserved.
语种	英语 ; 英语
出版者	ELSEVIER SCIENCE BV ; AMSTERDAM ; PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS
内容类型	期刊论文
源URL	[http://hdl.handle.net/123456789/13344]
专题	清华大学
推荐引用方式 GB/T 7714	Shi, Hong-Chang,Li, Yong. Formation of nitroxide radicals from secondary amines and peracids: A peroxyl radical oxidation pathway derived from electron spin resonance detection and density functional theory calculation[J],2010, 2010.
APA	Shi, Hong-Chang,&Li, Yong.(2010).Formation of nitroxide radicals from secondary amines and peracids: A peroxyl radical oxidation pathway derived from electron spin resonance detection and density functional theory calculation..
MLA	Shi, Hong-Chang,et al."Formation of nitroxide radicals from secondary amines and peracids: A peroxyl radical oxidation pathway derived from electron spin resonance detection and density functional theory calculation".(2010).

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