{"id":55214,"date":"2018-03-09T22:42:55","date_gmt":"2018-03-09T22:42:55","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/ciclorreversion-de-iones-radicales-de-oxetanos\/"},"modified":"2018-03-09T22:42:55","modified_gmt":"2018-03-09T22:42:55","slug":"ciclorreversion-de-iones-radicales-de-oxetanos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/fisica-molecular\/ciclorreversion-de-iones-radicales-de-oxetanos\/","title":{"rendered":"Ciclorreversi\u00f3n de iones radicales de oxetanos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Ra\u00fal P\u00e9rez Ruiz <\/strong><\/h2>\n<p>La ciclorreversi\u00f3n (cr) oxidativa \u00f3 reductiva de oxetanos por transferencia electr\u00f3nica fotoinducida (tef), no ha sido estudiada en profundidad, a pesar de que este proceso ha despertado un gran inter\u00e9s en la \u00faltima d\u00e9cada en relaci\u00f3n con la exploraci\u00f3n de nuevas rutas sint\u00e9ticas y con la reparaci\u00f3n fotoqu\u00edmica del adn.  respecto a la via fotooxidativa, teniendo en cuenta los c\u00e1lculos te\u00f3ricos y los datos experimentales ya publicados sobre su naturaleza se ha considerado interesante realizar un estudio experimental que aporte nuevos conocimientos acerca del mecanismo de reacci\u00f3n. En este contexto, se ha elegido como sustrato modelo el trans,trans-2-ciclopropil-3-fenil-4-metiloxetano (1) que ha permitido aclarar aspectos mecan\u00edsticos de la cr oxidativa de oxetanos. La escisi\u00f3n de 1 por ruptura inicial del enlace c2-c3 da lugar a los compuestos utilizados en la fotocicloadici\u00f3n de patero-b\u00ed\u00bcchi para la s\u00edntesis de 1. Por el contrario, la formaci\u00f3n de un fotoproducto nuevo debido a la captura nucleof\u00edlica intermolecular del intermedio resultante de la fragmentaci\u00f3n al enlace o-c2 por acetonitrilo est\u00e1 de acuerdo con un mecanismo por pasos. respecto a la via fotorreductiva, se ha estudiado la cr del  sustrato modelo trans,trans-2-(4-cianofenil)-3-fenil-4-metiloxetano (4) usando el 1-metoxinaftaleno como fotosensibilizador. Los datos experimentales son consistentes con que la reacci\u00f3n tiene lugar desde el estado singlete del sensibilizador. La fragmentaci\u00f3n del ani\u00f3n radical de 4 ocurre por ruptura de los enlaces o-c2 y c3-c4 dando lugar a productos (acetaldeh\u00eddo y 4-cianoestilbeno) diferentes a los usados para la s\u00edntesis de 4 por medio de la fotociloadici\u00f3n de paterno-b\u00ed\u00bcchi. El proceso transcurre a trav\u00e9s del ani\u00f3n radical del trans-4-cianoestilbeno, que se ha detectado mediante fdl (?Max = 500 nm).<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Ciclorreversi\u00f3n de iones radicales de oxetanos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Ciclorreversi\u00f3n de iones radicales de oxetanos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Ra\u00fal P\u00e9rez Ruiz <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Polit\u00e9cnica de Valencia<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 27\/10\/2006<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n<h3>Direcci\u00f3n y tribunal<\/h3>\n<ul>\n<li><strong>Director de la tesis<\/strong>\n<ul>\n<li>Miguel \u00e1ngel Miranda Alonso<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: gregorio Asensio aguilar <\/li>\n<li>julia P\u00e9rez prieto (vocal)<\/li>\n<li>athanasios Gkimisis (vocal)<\/li>\n<li>M\u00aa \u00e1ngeles Izquierdo arcusa (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Ra\u00fal P\u00e9rez Ruiz La ciclorreversi\u00f3n (cr) oxidativa \u00f3 reductiva de oxetanos por transferencia electr\u00f3nica fotoinducida (tef), no [&hellip;]<\/p>\n","protected":false},"author":1,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"site-sidebar-layout":"default","site-content-layout":"","ast-site-content-layout":"","site-content-style":"default","site-sidebar-style":"default","ast-global-header-display":"","ast-banner-title-visibility":"","ast-main-header-display":"","ast-hfb-above-header-display":"","ast-hfb-below-header-display":"","ast-hfb-mobile-header-display":"","site-post-title":"","ast-breadcrumbs-content":"","ast-featured-img":"","footer-sml-layout":"","theme-transparent-header-meta":"","adv-header-id-meta":"","stick-header-meta":"","header-above-stick-meta":"","header-main-stick-meta":"","header-below-stick-meta":"","astra-migrate-meta-layouts":"default","ast-page-background-enabled":"default","ast-page-background-meta":{"desktop":{"background-color":"var(--ast-global-color-4)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"ast-content-background-meta":{"desktop":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"tablet":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""},"mobile":{"background-color":"var(--ast-global-color-5)","background-image":"","background-repeat":"repeat","background-position":"center center","background-size":"auto","background-attachment":"scroll","background-type":"","background-media":"","overlay-type":"","overlay-color":"","overlay-gradient":""}},"footnotes":""},"categories":[1272,4709,16820],"tags":[121984,12080,43088,8213,65743,121983],"class_list":["post-55214","post","type-post","status-publish","format-standard","hentry","category-fisica-molecular","category-fotoquimica","category-politecnica-de-valencia","tag-athanasios-gkimisis","tag-gregorio-asensio-aguilar","tag-julia-perez-prieto","tag-miguel-angel-miranda-alonso","tag-ma-angeles-izquierdo-arcusa","tag-raul-perez-ruiz"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/55214","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/comments?post=55214"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/55214\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=55214"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=55214"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=55214"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}