{"id":117943,"date":"2018-03-11T10:47:44","date_gmt":"2018-03-11T10:47:44","guid":{"rendered":"https:\/\/www.deberes.net\/tesis\/sin-categoria\/nuevas-aplicaciones-del-cloral-en-la-sa%c2%adntesis-de-compuestos-heteroca%c2%adclicos-nitrogenados\/"},"modified":"2018-03-11T10:47:44","modified_gmt":"2018-03-11T10:47:44","slug":"nuevas-aplicaciones-del-cloral-en-la-sa%c2%adntesis-de-compuestos-heteroca%c2%adclicos-nitrogenados","status":"publish","type":"post","link":"https:\/\/www.deberes.net\/tesis\/quimica\/nuevas-aplicaciones-del-cloral-en-la-sa%c2%adntesis-de-compuestos-heteroca%c2%adclicos-nitrogenados\/","title":{"rendered":"Nuevas aplicaciones del cloral en la s\u00edntesis de compuestos heteroc\u00edclicos nitrogenados"},"content":{"rendered":"

Tesis doctoral de Enrique Alarc\u00f3n Belmonte <\/strong><\/h2>\n

Resumen se han desarrollado nuevos m\u00e9todos de s\u00edntesis para varias clases de compuestos heteroc\u00edclicos nitrogenados partiendo de derivados del cloral: pirimidinas, imidazo[1,5-b]pirazoles, imidazo[1,5-b][1,2,4]triazoles, 1,2,4-triazinas y 1,2,4-triazoles. se efectuaron reacciones entre cloral y acetofenonas que dieron lugar a cloralacetofenonas con elevados rendimientos, las cuales fueron eficazmente deshidratadas para dar 2,2,2-tricloroetilidenacetofenonas, que se hicieron reaccionar con benzamidinas para dar nuevas 2,6-diaril-6-hidroxi-4-triclorometil-1,4,5,6-tetrahidropirimidinas con rendimientos pr\u00e1cticamente cuantitativos. Estos compuestos fueron deshidratados eficazmente, obteni\u00e9ndose 2,4-diaril-6-triclorometil-1,6-dihidro-pirimidinas, sustancias previamente desconocidas, que se encontraron capaces de aromatizar, v\u00eda eliminaci\u00f3n de cloroformo, para dar 2,4-diarilpirimidinas con elevados rendimientos. La principal ventaja de este procedimiento radica en que permite eludir la deshidrogenaci\u00f3n oxidativa de dihidropirimidinas intermedias. Adicionalmente, este m\u00e9todo preparativo puede adaptarse a un protocolo "one-pot". Las estructuras moleculares de (4rs,6rs)-6-(4-clorofenil)-2-fenil-6-hidroxi-4-triclorometil-1,4,5,6-tetrahidropirimidina, 2-fenil-4-(4-nitrofenil)-6-triclorometil-1,6-dihidropirimidina y 4-(2-naftil)-2-(3-nitrofenil)pirimidina fueron determinadas mediante cristalograf\u00eda de rayos x. se ha conseguido la primera s\u00edntesis de 5-aril-2-hidroxi-4,5-dihidroimidazo[1,5-b]pirazol-6-onas. La reacci\u00f3n de 4,4,4-triclorocrotonato de etilo con hidracina proporcion\u00f3 un intermedio clave, 5-triclorometil-3-pirazolidona (87%), compuesto previamente desconocido cuyas reacciones con arilisocianatos proporcionaron 1-arilaminocarbonil-5-triclorometil-3-pirazolidonas (71-88%), que fueron transformadas en 1-arilaminocarbonil-5-diclorometil-3-pirazolidonas (80-91%) mediante reducci\u00f3n electroqu\u00edmica. Estos compuestos dieron lugar a los productos finales (62-80%) bajo condiciones fuertemente b\u00e1sicas. La estructura molecular de 5-fenil-2-hidroxi-4,5-dihidroimidazo[1,5-b]pirazol-6-ona fue determinada mediante cristalograf\u00eda de rayos x. Mediante una modificaci\u00f3n de este m\u00e9todo preparativo se consigui\u00f3 la primera s\u00edntesis de 2-aril-6-(4-toluenosulfonil)-6,7-dihidroimidazo[1,5-b][1,2,4]triazol-5-onas con rendimientos moderados. La estructura molecular de un miembro de esta nueva familia de compuestos, 2-(4-clorofenil)-6-(4-toluenosulfonil)-6,7-dihidroimidazo[1,5-b]-[1,2,4]triazol-5-ona, fue determinada mediante cristalograf\u00eda de rayos x. el tratamiento de 3-aril-5-diclorometil-?2-1,2,4-triazolinas (preparadas a partir de cloralamidas) con una base fuerte o una base d\u00e9bil deriv\u00f3 en procesos qu\u00edmicos radicalmente diferentes. Las reacciones con terc-but\u00f3xido pot\u00e1sico fueron r\u00e1pidas, llevando a 3-aril-1,2,4-triazinas (71-82%), siendo la primera observaci\u00f3n de una transformaci\u00f3n directa triazolina-triazina. Sin embargo, las reacciones con trietilamina fueron mucho m\u00e1s lentas, proporcionando nuevos 3-aril-5-diclorometil-1-(5-aril-1h-1,2,4-triazol-3-ilmetil)-1,2,4-triazoles (61-72%). La estructura molecular de 5-diclorometil-3-fenil-1-(5-fenil-1h-1,2,4-triazol-3-ilmetil)-1,2,4-triazol fue determinada mediante cristalograf\u00eda de rayos x. se efectuaron estudios te\u00f3ricos, basados en m\u00e9todos de funcional densidad (dft), de los mecanismos de reacci\u00f3n implicados en la s\u00edntesis de imidazopirazoles, triazinas y triazoles. abstract new synthetic methods for several classes of nitrogen-containing heterocyclic compounds including pyrimidines, imidazo[1,5-b]pyrazoles, imidazo[1,5-b][1,2,4]-triazoles, 1,2,4-triazines, and 1,2,4-triazoles have been developed starting from chloral derivatives. high yield reactions between chloral and acetophenones were carried out leading to chloralacetophenones, which were dehydrated effectively to give 2,2,2-trichloroethylideneacetophenones, that reacted with benzamidines leading to novel 2,6-diaryl-6-hydroxy-4-trichloromethyl-1,4,5,6-tetrahydropyrimidines in near quantitative yields. These compounds were efficiently dehydrated to obtain previously unknown 2,4-diaryl-6-trichloromethyl-1,6-dihydropyrimidines, which were found able to undergo aromatization via chloroform elimination to yield 2,4-diarylpyrimidines in high yields. A main improvement of this procedure lies in circumventing the oxidative dehydrogenation of dihydropyrimidine intermediates. This preparative process could also be adapted to a one-pot protocol. Molecular structures of (4rs,6rs)-6-(4-chlorophenyl)-2-phenyl-6-hydroxy-4-trichloromethyl-1,4,5,6-tetrahydro-pyrimidine, 2-phenyl-4-(4-nitrophenyl)-6-trichloromethyl-1,6-dihydro-pyrimidine, and 4-(2-naphthyl)-2-(3-nitrophenyl)pyrimidine were determined by x-ray crystallography. the first synthesis of 5-aryl-2-hydroxy-4,5-dihydroimidazo[1,5-b]pyrazol-6-ones was achieved. Ethyl 4,4,4,-trichlorocrotonate and hydrazine reacted to provide a previously unknown key synthetic intermediate, 5-trichloromethyl-3-pyrazolidone (87%), whose reactions with aryl isocyanates gave 1-arylaminocarbonyl-5-trichloromethyl-3-pyrazolidones (71-88%), which were converted to 1-aryl-aminocarbonyl-5-dichloromethyl-3-pyrazolidones (80-91%) by electrochemical reduction. These compounds led to the targeted products (62-80%) under strong basic conditions. The molecular structure of 5-phenyl-2-hydroxy-4,5-dihydroimidazo[1,5-b]-pyrazol-6-one was determined by x-ray crystallography. A successful modification of this preparative method allowed the first synthesis of 2-aryl-6-(4-toluenesulphonyl)-6,7-dihydroimidazo[1,5-b][1,2,4]triazol-5-ones in moderate yields. The molecular structure of a member of this new family of compounds, 2-(4-chlorophenyl)-6-(4-toluenesulphonyl)-6,7-dihydroimidazo[1,5-b][1,2,4]-triazol-5-one, was determined by x-ray crystallography. 3-aryl-5-dicloromethyl-?2-1,2,4-triazolines, prepared from chloralamides, were treated with either a strong base or a weak base undergoing completely different chemical processes. Fast reactions occurred with potassium tert-butoxide yielding 3-aryl-1,2,4-triazines (71-82%), it being the first time that a direct triazoline-triazine transformation was observed. However, reactions with triethylamine were observed to be much lower, leading to novel 3-aryl-5-dichloromethyl-1-(5-aryl-1h-1,2,4-triazol-3-ylmethyl)-1,2,4-triazoles (61-72%). The molecular structure of 5-dichloromethyl-3-phenyl-1-(5-phenyl-1h-1,2,4-triazol-3-ylmethyl)-1,2,4-triazol was determined by x-ray crystallography. theoretical studies based on density functional theory (dft) have been carried out on the reaction pathways leading to imidazopyrazoles, triazines and triazoles.<\/p>\n

 <\/p>\n

Datos acad\u00e9micos de la tesis doctoral \u00abNuevas aplicaciones del cloral en la s\u00edntesis de compuestos heteroc\u00edclicos nitrogenados<\/strong>\u00ab<\/h3>\n
    \n
  • T\u00edtulo de la tesis:<\/strong>\u00a0 Nuevas aplicaciones del cloral en la s\u00edntesis de compuestos heteroc\u00edclicos nitrogenados <\/li>\n
  • Autor:<\/strong>\u00a0 Enrique Alarc\u00f3n Belmonte <\/li>\n
  • Universidad:<\/strong>\u00a0 Murcia<\/li>\n
  • Fecha de lectura de la tesis:<\/strong>\u00a0 23\/07\/2015<\/li>\n<\/ul>\n

     <\/p>\n

    Direcci\u00f3n y tribunal<\/h3>\n
      \n
    • Director de la tesis<\/strong>\n
        \n
      • Antonio Guirado Moya<\/li>\n<\/ul>\n<\/li>\n
      • Tribunal<\/strong>\n
          \n
        • Presidente del tribunal: fructuoso Barba valiente <\/li>\n
        • pedro Antonio Garcia ruiz (vocal)<\/li>\n
        • belen Batanero hernan (vocal)<\/li>\n
        • Manuel Hern\u00e1ndez c\u00f3rdoba (vocal)<\/li>\n<\/ul>\n<\/li>\n<\/ul>\n

           <\/p>\n","protected":false},"excerpt":{"rendered":"

          Tesis doctoral de Enrique Alarc\u00f3n Belmonte Resumen se han desarrollado nuevos m\u00e9todos de s\u00edntesis para varias clases de compuestos heteroc\u00edclicos […]<\/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":[1424,8235,17,416],"tags":[31743,31679,232128,17672,12757,190585],"class_list":["post-117943","post","type-post","status-publish","format-standard","hentry","category-electroquimica","category-murcia","category-quimica","category-quimica-organica","tag-antonio-guirado-moya","tag-belen-batanero-hernan","tag-enrique-alarcon-belmonte","tag-fructuoso-barba-valiente","tag-manuel-hernandez-cordoba","tag-pedro-antonio-garcia-ruiz"],"_links":{"self":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/117943","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=117943"}],"version-history":[{"count":0,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/posts\/117943\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/media?parent=117943"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/categories?post=117943"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.deberes.net\/tesis\/wp-json\/wp\/v2\/tags?post=117943"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}