Síntese e estrutura de compostos poliaza heterocíclicos
Ano de defesa: | 2012 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4236 |
Resumo: | This work describes the synthesis of a number of polyaza heterocycles and the mechanistic study to obtain these products. Furthermore, the characterization was performed by spectroscopic method and the structural study by X-ray diffraction and theoretical calculations of molecular orbitals. The synthesis of polyaza heterocyclic compounds began from the cyclocondensation reaction between a β- enaminodiketone and 2-aminopyridine, 2-aminothiazole or 2-aminobenzoimidazole in order to achieve pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one or 2- oxo-pyrimido[1,2-a]benzimidazole, respectively, with a α-keto ester substituent, in high regioselectivity. The mechanistic proposal developed in this step is based on the semi-empirical theoretical calculations by the PM3 method. From these data it was possible to say that the reaction was controlled by frontier molecular orbital, according to values of HOMO/LUMO coefficient obtained for the reactants. In the next step, the α-keto esters previously obtained, were reacted with ethylenediamine and derivatives ledding to the pyrazinones formation and the reaction with 1,2- phenylenediamine and derivatives led to the formation quinoxalinones. The same reaction of α-keto esters with amidines did not lead to the formation of imidazolonas as expected, since only the formation of the substitution product in the ester group occurred. The reaction mechanisms proposed in these steps are also based in theoretical calculations, where it was possible to infer that the reaction was thermodynamically controlled, since the reactivity sites were less important than the stability of the intermediates. The compounds were characterized by 1D nuclear magnetic resonance experiments of such as 1H and 13C and 2D such as COSY, HETCOR and HMBC, besides of mass spectrometry. The molecular structural studies by X-ray diffraction (for the compounds that could be measured) revealed that polyaza heterocycles pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one and 2-oxo-pyrimido[1,2-a]benzimidazole are essentially plane. All these compounds showed as pattern at least one intramolecular interaction between a carbonyl oxygen atom and a carbonyl carbon via π-hole, forming a five membered pseudo-ring, which stabilizes the position of a carbonyl group. The study revealed that all structural supramolecular compounds exhibit a large number of weak hydrogen bonds of the type CH···X (where X = O, N) and the compounds which exhibited a NH group in its structure or water in the asymmetric unit formed additionally strong hydrogen bonds of the type X-H···X (where X = O, N). Since the structures studied are aromatic heterocycles, all compounds showed interactions involving π systems in their interactions like π···π and/or lone-pair···π in their crystal packing. Only one intermolecular interaction via σ-hole (C=O···S) and another via π-hole (C=O···C=O) were found. |
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2017-05-222017-05-222012-07-27CAMPOS, Patrick Teixeira. Synthesis and structure of compounds polyaza heterocyclic. 2012. 290 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012.http://repositorio.ufsm.br/handle/1/4236This work describes the synthesis of a number of polyaza heterocycles and the mechanistic study to obtain these products. Furthermore, the characterization was performed by spectroscopic method and the structural study by X-ray diffraction and theoretical calculations of molecular orbitals. The synthesis of polyaza heterocyclic compounds began from the cyclocondensation reaction between a β- enaminodiketone and 2-aminopyridine, 2-aminothiazole or 2-aminobenzoimidazole in order to achieve pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one or 2- oxo-pyrimido[1,2-a]benzimidazole, respectively, with a α-keto ester substituent, in high regioselectivity. The mechanistic proposal developed in this step is based on the semi-empirical theoretical calculations by the PM3 method. From these data it was possible to say that the reaction was controlled by frontier molecular orbital, according to values of HOMO/LUMO coefficient obtained for the reactants. In the next step, the α-keto esters previously obtained, were reacted with ethylenediamine and derivatives ledding to the pyrazinones formation and the reaction with 1,2- phenylenediamine and derivatives led to the formation quinoxalinones. The same reaction of α-keto esters with amidines did not lead to the formation of imidazolonas as expected, since only the formation of the substitution product in the ester group occurred. The reaction mechanisms proposed in these steps are also based in theoretical calculations, where it was possible to infer that the reaction was thermodynamically controlled, since the reactivity sites were less important than the stability of the intermediates. The compounds were characterized by 1D nuclear magnetic resonance experiments of such as 1H and 13C and 2D such as COSY, HETCOR and HMBC, besides of mass spectrometry. The molecular structural studies by X-ray diffraction (for the compounds that could be measured) revealed that polyaza heterocycles pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one and 2-oxo-pyrimido[1,2-a]benzimidazole are essentially plane. All these compounds showed as pattern at least one intramolecular interaction between a carbonyl oxygen atom and a carbonyl carbon via π-hole, forming a five membered pseudo-ring, which stabilizes the position of a carbonyl group. The study revealed that all structural supramolecular compounds exhibit a large number of weak hydrogen bonds of the type CH···X (where X = O, N) and the compounds which exhibited a NH group in its structure or water in the asymmetric unit formed additionally strong hydrogen bonds of the type X-H···X (where X = O, N). Since the structures studied are aromatic heterocycles, all compounds showed interactions involving π systems in their interactions like π···π and/or lone-pair···π in their crystal packing. Only one intermolecular interaction via σ-hole (C=O···S) and another via π-hole (C=O···C=O) were found.Neste trabalho é descrita a síntese de uma série de poliaza heterociclos e o estudo mecanístico para a obtenção destes produtos. Além disso, é realizada sua caracterização utilizando métodos espectroscópicos e o estudo estrutural por difração de Raios-X e cálculos teóricos de orbitais moleculares. A síntese dos compostos poliaza heterocíclicos teve inicio a partir de reações de ciclocondensação entre uma β-enaminodicetona e 2-aminopiridina, 2-aminotiazol ou 2-aminobenzoimidazol para obter pirido[1,2-a]pirimidin-4-ona, tiazolo[3,2-a]pirimidin-5- ona e 2-oxo-pirimido[1,2-a]benzoimidazol, respectivamente, com um substituinte α- ceto éster, de maneira altamente regiosseletiva. A proposta mecanística elaborada nesta etapa está embasada em cálculos teóricos semi-empíricos pelo método PM3. A partir destes dados é possível afirmar que a reação é controlada por orbital molecular de fronteira, conforme os valores de coeficiente de HOMO/LUMO obtidos para os reagentes. Na etapa seguinte, os α-ceto ésteres, previamente obtidos, ao reagirem com etilenodiamino e derivados levaram a formação de pirazinonas, bem como, a reação com 1,2-fenilenodiamino e derivados levou a formação de quinoxalinonas como produto. A reação dos mesmos α-ceto ésteres com amidinas não levou a formação de imidazolonas como desejado, pois ocorreu apenas a formação do produto de substituição no grupo éster. Os mecanismos de reação propostos nestas etapas também estão embasados em cálculos teóricos, onde foi possível inferir que a reação foi termodinamicamente controlada, já que, a reatividade dos sítios foi menos importante que a estabilidade dos intermediários. Os compostos foram caracterizados utilizando ressonância magnética nuclear em experimentos de 1D como 1H e 13C, e 2D como COSY, HETCOR e HMBC, além de espectrometria de massas. O estudo estrutural molecular por difração de Raios-x (referente aos compostos que puderam ser medidos) revelou que os poliaza heterociclos pirido[1,2- a]pirimidin-4-ona, tiazolo[3,2-a]pirimidin-5-ona e 2-oxo-pirimido[1,2-a]benzoimidazol são essencialmente planos. Um padrão observado nestes compostos é que todos apresentam, pelo menos, uma interação intramolecular entre um átomo de oxigênio carbonílico e um carbono carbonílico via π-hole, formando um pseudo-anel de cinco membros, que estabiliza a posição de uma carbonila. O estudo estrutural supramolecular revelou que todos os compostos apresentam um amplo número de ligações de hidrogênio fracas do tipo C-H· · ·X (quando, X = O, N) e os compostos que apresentaram um grupo N-H em sua estrutura ou água na unidade assimétrica formam, adicionalmente, ligações de hidrogênio fortes do tipo X-H···X (quando, X = O, N). Como as estruturas estudadas apresentam heterociclos aromáticos, todos os compostos mostraram interações envolvendo seus sistemas π em interações do tipo π· · ·π e/ou lone-pair· · ·π em seus empacotamentos cristalinos. Apenas uma interação intermolecular via σ-hole (C=O· · ·S) e uma via π-hole (C=O· · ·C=O) foram encontradas.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaPirido[1,2-a]pirimidinonaTiazolo[3,2-a]pirimidinonaPirimido[1,2- a]benzoimidazolPirazinonaQuinoxalinonaRMNRaios-XPM3Pyrido[1,2-a]pyrimidinoneThiazolo[3,2-a]pyrimidinonePyrimido[1,2-a]benzoimidazolePyrazinoneQuinoxalinoneNMRX-RayPM3CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese e estrutura de compostos poliaza heterocíclicosSynthesis and structure of compounds polyaza heterocyclicinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, Marcos Antonio Pintohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3Siqueira, Geonir Machadohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774H9Rosa, Fernanda Andreiahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4772056D8Flores, Alex Fabiani Clarohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774Y0Zanatta, Nilohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4594570D4Campos, Patrick Teixeira100600000000400300300300300300300c28419d9-6027-4f9c-acd2-76e8067a85d1c2c55a9e-8ad6-49d1-943c-06500fac843da38d50c4-7cd2-4e3c-a998-d44fbb5ca4add8662a5f-28f9-41c1-a6af-67b2581ef1d4ef88f877-9177-4caf-ba05-4129d89287e1db72aa79-2ac0-4a18-90a9-823ea140938ainfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALCAMPOS, PATRICK TEIXEIRA.pdfapplication/pdf36986969http://repositorio.ufsm.br/bitstream/1/4236/1/CAMPOS%2c%20PATRICK%20TEIXEIRA.pdfa4dcc4836ed8ebb74131a9f91a3ba399MD51TEXTCAMPOS, PATRICK TEIXEIRA.pdf.txtCAMPOS, PATRICK TEIXEIRA.pdf.txtExtracted texttext/plain334435http://repositorio.ufsm.br/bitstream/1/4236/2/CAMPOS%2c%20PATRICK%20TEIXEIRA.pdf.txtb58d83ce578e01a134e0ec4b6ed563ceMD52THUMBNAILCAMPOS, PATRICK TEIXEIRA.pdf.jpgCAMPOS, PATRICK TEIXEIRA.pdf.jpgIM Thumbnailimage/jpeg5933http://repositorio.ufsm.br/bitstream/1/4236/3/CAMPOS%2c%20PATRICK%20TEIXEIRA.pdf.jpgd5a392d97eede0a2f4d5093f164cc55cMD531/42362017-07-25 11:05:13.634oai:repositorio.ufsm.br:1/4236Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:13Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese e estrutura de compostos poliaza heterocíclicos |
dc.title.alternative.eng.fl_str_mv |
Synthesis and structure of compounds polyaza heterocyclic |
title |
Síntese e estrutura de compostos poliaza heterocíclicos |
spellingShingle |
Síntese e estrutura de compostos poliaza heterocíclicos Campos, Patrick Teixeira Pirido[1,2-a]pirimidinona Tiazolo[3,2-a]pirimidinona Pirimido[1,2- a]benzoimidazol Pirazinona Quinoxalinona RMN Raios-X PM3 Pyrido[1,2-a]pyrimidinone Thiazolo[3,2-a]pyrimidinone Pyrimido[1,2-a]benzoimidazole Pyrazinone Quinoxalinone NMR X-Ray PM3 CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e estrutura de compostos poliaza heterocíclicos |
title_full |
Síntese e estrutura de compostos poliaza heterocíclicos |
title_fullStr |
Síntese e estrutura de compostos poliaza heterocíclicos |
title_full_unstemmed |
Síntese e estrutura de compostos poliaza heterocíclicos |
title_sort |
Síntese e estrutura de compostos poliaza heterocíclicos |
author |
Campos, Patrick Teixeira |
author_facet |
Campos, Patrick Teixeira |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Martins, Marcos Antonio Pinto |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3 |
dc.contributor.referee1.fl_str_mv |
Siqueira, Geonir Machado |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774H9 |
dc.contributor.referee2.fl_str_mv |
Rosa, Fernanda Andreia |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4772056D8 |
dc.contributor.referee3.fl_str_mv |
Flores, Alex Fabiani Claro |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4782774Y0 |
dc.contributor.referee4.fl_str_mv |
Zanatta, Nilo |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783100P9 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4594570D4 |
dc.contributor.author.fl_str_mv |
Campos, Patrick Teixeira |
contributor_str_mv |
Martins, Marcos Antonio Pinto Siqueira, Geonir Machado Rosa, Fernanda Andreia Flores, Alex Fabiani Claro Zanatta, Nilo |
dc.subject.por.fl_str_mv |
Pirido[1,2-a]pirimidinona Tiazolo[3,2-a]pirimidinona Pirimido[1,2- a]benzoimidazol Pirazinona Quinoxalinona RMN Raios-X PM3 |
topic |
Pirido[1,2-a]pirimidinona Tiazolo[3,2-a]pirimidinona Pirimido[1,2- a]benzoimidazol Pirazinona Quinoxalinona RMN Raios-X PM3 Pyrido[1,2-a]pyrimidinone Thiazolo[3,2-a]pyrimidinone Pyrimido[1,2-a]benzoimidazole Pyrazinone Quinoxalinone NMR X-Ray PM3 CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Pyrido[1,2-a]pyrimidinone Thiazolo[3,2-a]pyrimidinone Pyrimido[1,2-a]benzoimidazole Pyrazinone Quinoxalinone NMR X-Ray PM3 |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work describes the synthesis of a number of polyaza heterocycles and the mechanistic study to obtain these products. Furthermore, the characterization was performed by spectroscopic method and the structural study by X-ray diffraction and theoretical calculations of molecular orbitals. The synthesis of polyaza heterocyclic compounds began from the cyclocondensation reaction between a β- enaminodiketone and 2-aminopyridine, 2-aminothiazole or 2-aminobenzoimidazole in order to achieve pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one or 2- oxo-pyrimido[1,2-a]benzimidazole, respectively, with a α-keto ester substituent, in high regioselectivity. The mechanistic proposal developed in this step is based on the semi-empirical theoretical calculations by the PM3 method. From these data it was possible to say that the reaction was controlled by frontier molecular orbital, according to values of HOMO/LUMO coefficient obtained for the reactants. In the next step, the α-keto esters previously obtained, were reacted with ethylenediamine and derivatives ledding to the pyrazinones formation and the reaction with 1,2- phenylenediamine and derivatives led to the formation quinoxalinones. The same reaction of α-keto esters with amidines did not lead to the formation of imidazolonas as expected, since only the formation of the substitution product in the ester group occurred. The reaction mechanisms proposed in these steps are also based in theoretical calculations, where it was possible to infer that the reaction was thermodynamically controlled, since the reactivity sites were less important than the stability of the intermediates. The compounds were characterized by 1D nuclear magnetic resonance experiments of such as 1H and 13C and 2D such as COSY, HETCOR and HMBC, besides of mass spectrometry. The molecular structural studies by X-ray diffraction (for the compounds that could be measured) revealed that polyaza heterocycles pyrido[1,2-a]pyrimidin-4-one, thiazole[3,2-a]pyrimidin-5-one and 2-oxo-pyrimido[1,2-a]benzimidazole are essentially plane. All these compounds showed as pattern at least one intramolecular interaction between a carbonyl oxygen atom and a carbonyl carbon via π-hole, forming a five membered pseudo-ring, which stabilizes the position of a carbonyl group. The study revealed that all structural supramolecular compounds exhibit a large number of weak hydrogen bonds of the type CH···X (where X = O, N) and the compounds which exhibited a NH group in its structure or water in the asymmetric unit formed additionally strong hydrogen bonds of the type X-H···X (where X = O, N). Since the structures studied are aromatic heterocycles, all compounds showed interactions involving π systems in their interactions like π···π and/or lone-pair···π in their crystal packing. Only one intermolecular interaction via σ-hole (C=O···S) and another via π-hole (C=O···C=O) were found. |
publishDate |
2012 |
dc.date.issued.fl_str_mv |
2012-07-27 |
dc.date.accessioned.fl_str_mv |
2017-05-22 |
dc.date.available.fl_str_mv |
2017-05-22 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
CAMPOS, Patrick Teixeira. Synthesis and structure of compounds polyaza heterocyclic. 2012. 290 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4236 |
identifier_str_mv |
CAMPOS, Patrick Teixeira. Synthesis and structure of compounds polyaza heterocyclic. 2012. 290 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2012. |
url |
http://repositorio.ufsm.br/handle/1/4236 |
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por |
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dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
BR |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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