Kinetic applications of electron paramagnetic resonance spectroscopy. 28. N-alkoxy-N-alkylamino, N-alkoxyamino, and N-alkoxyanilino radicals

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DOIResolve DOI: http://doi.org/10.1021/ja00439a045
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume98
Issue23
Pages73757380; # of pages: 6
AbstractRadicals of the types mentioned in the title have been generated and the kinetics and products of their decay have been examined. N-Alkoxy-N-alkylamino, ROṄR′, and N-alkoxyamino, ROṄH, radicals decay with second-order kinetics at about 10% of the diffusion-controlled rate. N-Alkoxyanilino radicals, ROṄC6H5, are much more persistent, they decay with first-order kinetics and exist in equilibrium with their dimers, ΔH ∼ 13.5 kcal/mol. N-Alkoxyaminos yield alcohols as the only organic products of decay, and N-ethoxyanilino yields only ethanol and trans-azobenzene. N-Alkoxy-N-alkylamino radicals generally yielded complex mixtures of products. However, N-benzyloxy-N-benzylamino gave approximately equimolar amounts of O-benzylbenzaldoxime, benzyl alcohol, benzaldehyde, and ω,ω′-azotoluene. The first of these products must arise by disproportionate. It is proposed that the other three products are formed via a Russell-type six-center concerted decomposition of an N-N coupled product. This type of decay appears to be confined to N-benzyloxy-N-alkylamino radicals, presumably because the benzylic hydrogens are activated by the adjacent phenyl group.
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LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276523
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Record identifierccb29538-0522-4a22-b9fe-93189671a458
Record created2015-10-13
Record modified2016-05-09
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