{"id":129591,"date":"1996-01-01T00:00:00","date_gmt":"1996-01-01T00:00:00","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/estudio-cinetico-de-la-nitrosacion-de-aminoacidos\/"},"modified":"1996-01-01T00:00:00","modified_gmt":"1996-01-01T00:00:00","slug":"estudio-cinetico-de-la-nitrosacion-de-aminoacidos","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/fisica\/estudio-cinetico-de-la-nitrosacion-de-aminoacidos\/","title":{"rendered":"Estudio cinetico de la nitrosacion de aminoacidos"},"content":{"rendered":"<h2>Tesis doctoral de <strong> Rafael Gil Gonzalez <\/strong><\/h2>\n<p>Con objeto de clarificar las analogias y diferencias entre los mecanismos de nitrosacion de sminoacidos y aminas secundarias, se han estudiado cineticamente las reacciones entre acido nitroso y acidos acetidin-2- carboxilico, acetidin-3-carboxilico, pirrolidin-2icarboxilico, piperidin-2- carboxilico, piperidin-3-carboxilico, piperidin-4-carboxilico, indolin-2- carboxilico, fenila,ompacetico, metilaminobutirico y metilaminoisobutirico, asi como de los esteres eitlicos de tres de ellos. Se ha utilizado un metodo de velocidades iniciales, evaluando espectrofotometricamente la concentracion de nitrosocompuestro formado. Los parametros cineticos se han calculado mediante un metodo de optimizacion no lineal.  la presencia del grupo -coo- en las moleculas de los substratos nitrosables abre una nueva via mecanistica en la nitrosacion del grupo amino: inicialmente se forma un aminocarboxilato de nitrosilo que actua como agente nitrosante interno, por migracion del grupo -no desde el grupo carboxilato hasta el aminosecundario. La secuencia de reactividadees observada (        aminoacidos) se ha interpretado sobre la base de los cambios de energia asociados a la estereoquimica de la transferencia intramolecular del grupo no. En los aminoacidos el proceso de migracion del grupo-n=o implica la formacion de una estructura pentagonal, estericamente favorecida.  en el   -aminoacido ese mecanismo exige la formacion de un ciclo hexagonal intermedio que requiere un reordenamiento previo del enlace canillo-ccarboxilo desde conformacion ecuatorial a una orientacion axial mas energetica. En cuanto al    aminoacido (intermedio heptagonal), se requiere no solo un cambio en el enlace canillo-ccarboxilo de orientacion ecuatorial a axial, sino tambien la conversion del anillo piperidinico de corformacion en silla a conformacion en barca, proceso que exigiria unaenergia adicional y, en consecuencia, determinara que el proceso este menos favorecido. Las e<\/p>\n<p>&nbsp;<\/p>\n<h3>Datos acad\u00e9micos de la tesis doctoral \u00ab<strong>Estudio cinetico de la nitrosacion de aminoacidos<\/strong>\u00ab<\/h3>\n<ul>\n<li><strong>T\u00edtulo de la tesis:<\/strong>\u00a0 Estudio cinetico de la nitrosacion de aminoacidos <\/li>\n<li><strong>Autor:<\/strong>\u00a0 Rafael Gil Gonzalez <\/li>\n<li><strong>Universidad:<\/strong>\u00a0 Salamanca<\/li>\n<li><strong>Fecha de lectura de la tesis:<\/strong>\u00a0 01\/01\/1996<\/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>Julio Casado Linarejos<\/li>\n<\/ul>\n<\/li>\n<li><strong>Tribunal<\/strong>\n<ul>\n<li>Presidente del tribunal: Salvador Senent P\u00e9rez <\/li>\n<li> Andres Ordax Francisco Jos\u00e9 (vocal)<\/li>\n<li>Licesio Rodriguez Hernandez (vocal)<\/li>\n<li>Jos\u00e9 Mar\u00eda Leal Villalba (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n<p>&nbsp;<\/p>\n","protected":false},"excerpt":{"rendered":"<p>Tesis doctoral de Rafael Gil Gonzalez Con objeto de clarificar las analogias y diferencias entre los mecanismos de nitrosacion de [&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 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