La transposición N-ciclopropilimina-1-pirrolina
In this work, it has been studied the rearrangement of N-cyclopropylimines to 1- pyrrolines which involves a type of aza(vinylcyclopropane-cyclopentene) rearrangement. It has been explored in its photochemical fashion, which constitutes a new reaction not described up to date, as well as the thermal...
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Universidad de La Rioja (España)
2004
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In this work, it has been studied the rearrangement of N-cyclopropylimines to 1- pyrrolines which involves a type of aza(vinylcyclopropane-cyclopentene) rearrangement. It has been explored in its photochemical fashion, which constitutes a new reaction not described up to date, as well as the thermal rearrangement, which has been previously explored only in a very limited extent. As a result, it has been synthesized a number of 1-pyrrolines in a quite simple way, with synthetically useful yields, exploring different patterns of substitution on the N-cyclopropylimine template.
Also, it has been studied the mechanism of the photoprocess, using a classical approach (products study, kinetics, solvent effect, selectivity, etc.) and from a theoretical point of view, to calculate energies of excited states, potential energy surfaces and conical intersections.
As a result of this combined study, it can be concluded a whole mechanistic proposal for the photorearrangement: a non-concerted direct process without reaction intermediates (thus, an ultrarrapid process in the time scale of picoseconds), but with diradical character in the calculated structures in the potential energy surface of the S1 state. From that state, the structure of the conical intersection between S1 and S0 determines the efficiency of the reaction and the product distribution (deactivation of the excited state, isomerization of the cyclopropane, rearrangement to the pyrroline and the selectivity of the latter process). |
| author2 |
Campos García, Pedro José (Universidad de La Rioja) |
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Campos García, Pedro José (Universidad de La Rioja) Soldevilla Armas, Alberto |
| format |
text (thesis) |
| author |
Soldevilla Armas, Alberto |
| spellingShingle |
Soldevilla Armas, Alberto La transposición N-ciclopropilimina-1-pirrolina |
| author_sort |
Soldevilla Armas, Alberto |
| title |
La transposición N-ciclopropilimina-1-pirrolina |
| title_short |
La transposición N-ciclopropilimina-1-pirrolina |
| title_full |
La transposición N-ciclopropilimina-1-pirrolina |
| title_fullStr |
La transposición N-ciclopropilimina-1-pirrolina |
| title_full_unstemmed |
La transposición N-ciclopropilimina-1-pirrolina |
| title_sort |
la transposición n-ciclopropilimina-1-pirrolina |
| publisher |
Universidad de La Rioja (España) |
| publishDate |
2004 |
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https://dialnet.unirioja.es/servlet/oaites?codigo=101 |
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AT soldevillaarmasalberto latransposicionnciclopropilimina1pirrolina |
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1718346547668713472 |
| spelling |
oai-TES00000000182016-04-13La transposición N-ciclopropilimina-1-pirrolinaSoldevilla Armas, AlbertoIn this work, it has been studied the rearrangement of N-cyclopropylimines to 1- pyrrolines which involves a type of aza(vinylcyclopropane-cyclopentene) rearrangement. It has been explored in its photochemical fashion, which constitutes a new reaction not described up to date, as well as the thermal rearrangement, which has been previously explored only in a very limited extent. As a result, it has been synthesized a number of 1-pyrrolines in a quite simple way, with synthetically useful yields, exploring different patterns of substitution on the N-cyclopropylimine template. Also, it has been studied the mechanism of the photoprocess, using a classical approach (products study, kinetics, solvent effect, selectivity, etc.) and from a theoretical point of view, to calculate energies of excited states, potential energy surfaces and conical intersections. As a result of this combined study, it can be concluded a whole mechanistic proposal for the photorearrangement: a non-concerted direct process without reaction intermediates (thus, an ultrarrapid process in the time scale of picoseconds), but with diradical character in the calculated structures in the potential energy surface of the S1 state. From that state, the structure of the conical intersection between S1 and S0 determines the efficiency of the reaction and the product distribution (deactivation of the excited state, isomerization of the cyclopropane, rearrangement to the pyrroline and the selectivity of the latter process).En este trabajo se ha estudiado el proceso de transposición de las N-ciclopropiliminas a 1-pirrolinas, que supone un tipo de transposición aza(vinilciclopropano-ciclopenteno). Se ha explorado en su versión fotoquímica, que constituye una reacción inédita hasta ahora, así como la transposición térmica, que había sido estudiada previamente sólo de modo muy limitado. Como resultado, se ha sintetizado un buen número de 1-pirrolinas de un modo bastante simple, con rendimientos útiles desde el punto de vista de la síntesis, explorando diferentes patrones de sustutución de la subestructura de N-ciclopropilimina. También se ha investigado el mecanismo del fotoproceso, empleando una aproximación clásica (estudio de productos, estudios cinéticos, efecto del disolvente, análisis de la selectividad, etc.) y, desde un punto de vista teórico, usando las técnicas computacionales (principalmente la estrategia CASPT2//CASSCF) para calcular energías de los estados excitados, superficies de energía potencial e intersecciones cónicas. Como resultado de este estudio combinado, se ha elaborado una propuesta mecanística completa para la fotorreacción: un proceso directo, no concertado, sin intermedios de reacción (y, por tanto, un proceso ultrarrápido, en el orden de los picosegundos), pero con carácter de birradical en las estructuras calculadas en la superficie de energía potencial del estado S1. A partir de ese estado, la estructura de la intersección cónica entre S1 y S0 determina la eficacia de la reacción y la distribución de los fotoproductos (desactivación del estado excitado, isomerización del ciclopropano, transposición a la 1-pirrolina y la selectividad de este proceso).Universidad de La Rioja (España)Campos García, Pedro José (Universidad de La Rioja)Rodríguez Barranco, Miguel Angel (Universidad de La Rioja)2004text (thesis)application/pdf(Tesis) ISBN 84-688-7027-7 https://dialnet.unirioja.es/servlet/oaites?codigo=101spaLICENCIA DE USO: Los documentos a texto completo incluidos en Dialnet son de acceso libre y propiedad de sus autores y/o editores. Por tanto, cualquier acto de reproducción, distribución, comunicación pública y/o transformación total o parcial requiere el consentimiento expreso y escrito de aquéllos. Cualquier enlace al texto completo de estos documentos deberá hacerse a través de la URL oficial de éstos en Dialnet. Más información: https://dialnet.unirioja.es/info/derechosOAI | INTELLECTUAL PROPERTY RIGHTS STATEMENT: Full text documents hosted by Dialnet are protected by copyright and/or related rights. This digital object is accessible without charge, but its use is subject to the licensing conditions set by its authors or editors. Unless expressly stated otherwise in the licensing conditions, you are free to linking, browsing, printing and making a copy for your own personal purposes. All other acts of reproduction and communication to the public are subject to the licensing conditions expressed by editors and authors and require consent from them. Any link to this document should be made using its official URL in Dialnet. More info: https://dialnet.unirioja.es/info/derechosOAI |