Síntesis de compuestos heterocíclicos utilizando catalizadores heterogéneos mono y multifuncionales
[EN] During the 1980s a new philosophy of chemical research and engineering gave rise, the so-called \Green Chemistry", and made both society and the industry aware of the need for a change. In this sense, catalysis provides the necessary tools for improving industrial processes as well as...
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| Formato: | tesis doctoral |
| Fecha de publicación: | 2015 |
| País: | España |
| Recursos: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | español |
| OAI Identifier: | oai:riunet.upv.es:10251/56146 |
| Acesso em linha: | https://riunet.upv.es/handle/10251/56146 |
| Access Level: | acceso abierto |
| Palavra-chave: | Catálisis Heterogénea Química Fina Reacciones multietapa Compuestos heterocíclicos QUIMICA ORGANICA |
| Resumo: | [EN] During the 1980s a new philosophy of chemical research and engineering gave rise, the so-called \Green Chemistry", and made both society and the industry aware of the need for a change. In this sense, catalysis provides the necessary tools for improving industrial processes as well as laboratory-scale ones. Speci cally, heterogeneous catalysis allows a signi cant saving both economically and environmentally, since it decreases the number of separation steps, which results in a smaller amount of byproducts and allows an easier retrieval of the catalyst. Within Chemistry, the elds of Fine and Pharmaceutical Chemistry require a greater e ort in order to reduce the E Factor. An approach for this task implies the design of multifunctional-character catalysts in order to perform multi-stage processes which combines several reaction steps into the same container. This avoids the isolation of intermediate products and ultimately translates into economical and envorimental savings. In this dissertation the synthesis of pharmaceutically-relevant heterocyclic compounds by multi-stage processes have been carried out. For each process an optimum multifunctional-character catalyst has been properly designed. The synthesis of 2,3-dihydro-4(1H)quinolinones, which ful ll many biological activities, has been performed. For this issue the preparation of 2'-aminochalcones, namely their precursors, was studied by means of a multi-stage process. A Claisen-Schmidt condensation between onitroacetophenone and benzaldehyde was rstly made, followed by a selective reduction of the nitro functional group to an amine group. This was accomplished by means of a bi-functional catalyst combining a basic metal oxide and a metal. After the optimization of the synthesis procedure for 2'-aminochalcones, a study of their intramolecular cyclization in order to yield dihydroquinolinones was carried out. This was accomplished by using mesoporous allumino-silicates as acid catalysts. Besides, a multi-stage process was achieved for obtaining dihydroquinolinones from 2'-nitrochalcones by combining metal and acid catalysts. Benzothiazepines, which are highly relevant in the pharmaceutical industry as psychotherapeutic drugs and are also related to the circulatory system, have been synthesized by cyclic condensation of chalcones with 2-aminothiophenol using as an optimum catalyst the mesoporous alluminosilicate MCM- 41. To this regard, a multi-stage process for obtaining benzothiacepines has been designed both in batch and continuous reactors, which has as a rst step the production of chalcone by means of a Claisen-Schmidt condensation between benzaldehyde and acetophenone using a basic catalyst (MgO), and a second step consisting of a cyclic condensation between the chalcone and 2-aminophenol aided by MCM-41 as an acid catalyst. Finally 2,1-benzisoxazoles derivatives, pharmaceutical drugs which act as anti-in ammatories in central nervous system diseases, have been synthesized, and excellent yields and selectivities have been obtained. The synthesis used as precursors o-nitroacyl-aromatic-type compounds and employed supported-metal catalysts. The process consists of a cascadetype reaction in which a selective reduction of the nitro functional group to hydoxylamine is performed, followed by a nucleophylic attack from the latter to the carbonyl group. Subsequent cyclization and dehydration yields to the ring of 2,1-benzisoxazole. |
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