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 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
Signaler une correction	Signaler une correction (s'ouvre dans un nouvel onglet)
Identificateur de l’enregistrement	2daa1a49-2b00-457f-b9e7-f6f89f389be9
Enregistrement créé	2015-10-13
Enregistrement modifié	2020-03-13

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