Kinetic applications of electron paramagnetic resonance spectroscopy. 36. Stereoelectronic effects in hydrogen atom abstraction from ethers

DOI	Trouver le DOI : https://doi.org/10.1021/ja00393a018
Auteur	Rechercher : Malatesta, V.¹; Rechercher : Ingold, K. U.¹
Affiliation	Conseil national de recherches du Canada
Format	Texte, Article
Résumé	Relative rates of hydrogen atom abstraction by photogenerated tert-butoxyl from a variety of cyclic and acyclic ethers, acetals, and orthoformates have been measured at -60°C by an EPR spectroscopic technique. There is a pronounced stereoelectronic effect which produces high rates of abstraction from those C-H bonds adjacent to oxygen which have a relatively small dihedral angle (ca. 30°) with respect to the p-type orbital(s) on the oxygen(s). For C-H bonds which have a large dihedral angle (ca. 90°) abstraction is very much slower. The barrier to inversion of the 2-methoxy-1,3-dioxolan-2-yl radical is ≥10 kcal/mol. © 1981 American Chemical Society.
Date de publication	1981
Dans	Journal of the American Chemical Society 103, nº 3 (1981) : 609–614.
Langue	anglais
Publications évaluées par des pairs	Oui
Numéro NPARC	21276607
Exporter la notice	Exporter en format RIS
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Identificateur de l’enregistrement	2daa1a49-2b00-457f-b9e7-f6f89f389be9
Enregistrement créé	2015-10-13
Enregistrement modifié	2020-03-13