## Abstract Photochemical or thermal decomposition of azo‐compounds (such as 2,2^′^‐azobisisobutyronitrile, 2,2^′^‐azobis(2‐methylpropionamidine) dihydrochloride, dialkyl peroxides (such as __tert__‐butyl peroxide and diacyl peroxides (such as benzoyl peroxide) in anaerobic nitric oxide (NO)‐satura
EPR study of nitroxides formed from the reaction of nitric oxide with photolyzed amides
✍ Scribed by Fan Wang; Jing Jin; Longmin Wu
- Publisher
- John Wiley and Sons
- Year
- 2003
- Tongue
- English
- Weight
- 271 KB
- Volume
- 41
- Category
- Article
- ISSN
- 0749-1581
- DOI
- 10.1002/mrc.1229
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✦ Synopsis
Abstract
Free radicals generated from UV irradiation of simple aliphatic amides in anaerobic and nitric oxide (NO)‐saturated liquid mixtures or solutions gave EPR spectra of nitroxides. The application of isotopic effects to EPR spectra and the generation of radicals by transient radical attack on substrate molecules or by photolysing amine or acetoin were used to help identify photochemically produced radicals from the amides. The aliphatic amides used were formamide, acetamide and their N‐methyl‐ or deuterium‐substituted derivatives. Transient radicals used to attack the amides via hydrogen‐atom abstraction were generated from the initiator AIBN or AAPH. The observation of various nitroxides indicates the reactivity of NO for trapping acyl, carbamoyl and other carbon‐centered radicals. Possibly mechanistic pathways diagnosed with this trap are proposed. Copyright © 2003 John Wiley & Sons, Ltd.
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## Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
The photoreaction of systems containing N-oxides and amines has been studied by ESR. The lowest triplet state of the heteroaromatic N-oxide combines with triethylamine to form an exciplex. Oxygen transfer and a-cleavage of the N-C bond in the amine part of the exciplex gave diethyl nitroxide.