Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas
Autor(a) principal: | |
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Data de Publicação: | 2016 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/10616 |
Resumo: | The present dissertation initially describes new methods for the synthesis of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane], as new trifluoromethyl substituted heterocyclic systems. Cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(1-methoxy-3,4-dihydronaphthalen-2-yl)ethanone and five amidines [NH2-(C=NH)R] conducted to the synthesis of a new series of five examples of 2-substituted 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines in 40-70% yield, where R = 2-substituent = H, methyl, phenyl, NH2 or SCH3. In sequence, a new series of nine unpublished 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane] were obtained in 73-95% yield from cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(4-methoxyspiro[chromene-2,1'-cycloalkane]-3-yl)ethanones and some amidines. These new spiro-heterocyclic structures have a methyl, phenyl or NH2 substituent attached to the position-2 and a 5-, 6- or 7-membered cycloalkane at the spiroposition-5, simultaneously. Finally, to demonstrate the synthetic utility of the 2-amino substituent attached to the obtained heterocycles, N-derivatization reactions of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolin-2-amine and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidine-5,1'-cyclopentan]-2-amines employing 2,5-dimethoxytetrahydrofuran in acetic acid medium (Clauson-Kaas reaction) by two methods are described. The first method followed a two-step reaction procedure (35-55%) and the second an "one pot" method (45-55%). The "one-pot" method was the most advantageous by some experimental aspects. However, both methods allowed an efficient conversion of the 2-amino group into the 2-(1H-pyrrol-1-yl) substituent and the obtainment of four new examples of 2- (1H-pyrrol-yl)-substituted heterocyclic molecules. |
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2017-05-262017-05-262016-02-23ROSA, Wilian Carvalho da. Synthesis of spiro[chromene[4,3-d]Pyrimidines-5,1'-cycloalkane] and 5,6-dihydrobenzo[h]quinazolines trifluoromethyl substituted. 2016. 187 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016.http://repositorio.ufsm.br/handle/1/10616The present dissertation initially describes new methods for the synthesis of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane], as new trifluoromethyl substituted heterocyclic systems. Cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(1-methoxy-3,4-dihydronaphthalen-2-yl)ethanone and five amidines [NH2-(C=NH)R] conducted to the synthesis of a new series of five examples of 2-substituted 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines in 40-70% yield, where R = 2-substituent = H, methyl, phenyl, NH2 or SCH3. In sequence, a new series of nine unpublished 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane] were obtained in 73-95% yield from cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(4-methoxyspiro[chromene-2,1'-cycloalkane]-3-yl)ethanones and some amidines. These new spiro-heterocyclic structures have a methyl, phenyl or NH2 substituent attached to the position-2 and a 5-, 6- or 7-membered cycloalkane at the spiroposition-5, simultaneously. Finally, to demonstrate the synthetic utility of the 2-amino substituent attached to the obtained heterocycles, N-derivatization reactions of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolin-2-amine and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidine-5,1'-cyclopentan]-2-amines employing 2,5-dimethoxytetrahydrofuran in acetic acid medium (Clauson-Kaas reaction) by two methods are described. The first method followed a two-step reaction procedure (35-55%) and the second an "one pot" method (45-55%). The "one-pot" method was the most advantageous by some experimental aspects. However, both methods allowed an efficient conversion of the 2-amino group into the 2-(1H-pyrrol-1-yl) substituent and the obtainment of four new examples of 2- (1H-pyrrol-yl)-substituted heterocyclic molecules.A presente dissertação descreve, inicialmente, metodologias para a síntese de sistemas espiro[cromeno[4,3-d]pirimidinas-5,1‟-cicloalcano] e 5,6-diidrobenzo[h]quinazolinas, ambos trifluormetil-substituídos. Reações de ciclocondensação do tipo [3+3] entre 1-metóxi-2-trifluoracetil-3,4-diidro-naftaleno e diferentes amidinas conduziu à síntese de uma série de cinco 5,6-diidrobenzo[h]quinazolinas 2-substituídas (40-70 %), onde 2-substituinte = H, Metila, Fenila, NH2 e SCH3. Na sequência, obteve-se uma série de nove espiro[cromeno[4,3-d]pirimidinas-5,1‟-cicloalcano] (73-95 %) a partir de reações de ciclocondensação do tipo [3+3] envolvendo 2,2,2-triflúor-1-[4-metóxi-espiro(2H-cromen-2,1‟-cicloalcan)-3- il]etanonas e amidinas. Estas estruturas espiro-heterocíclicas apresentam substituintes metila, fenila e NH2 na posição 2 e um espiro-cicloalcano de 5, 6 ou 7 carbonos na posição 5. Finalmente, descreve-se reações de N-derivatização de 2-amino-4-(trifluormetil)-5,6-diidrobenzo[h]quinazolina e 2-amino-4-(trifluormetil)-espiro-[cromeno[4,3-d]pirimidinas-5,1'-cicloalcano] com 2,5-dimetoxitetrahidrofurano em meio ácido acético (Reação de Clauson-Kaas) por dois métodos. O primeiro método em duas etapas (35-55%) e o segundo na forma one pot (45-55%). O método one-pot foi o mais vantajoso em vários aspectos experimentais, porém ambos permitiram a inserção do substituinte 1H-pirrol-1-ila e a obtenção de quatro moléculas heterocíclicas 2-(1H-pirrol-il)-substituídas.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídasSynthesis of spiro[chromene[4,3-d]Pyrimidines-5,1'-cycloalkane] and 5,6-dihydrobenzo[h]quinazolines trifluoromethyl substitutedinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisBonacorso, Helio Gauzehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0Zeni, Gilson Rogériohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6Severo Filho, Wolmar Alípiohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4790001P6http://lattes.cnpq.br/0155076624561301Rosa, Wilian Carvalho da10060000000040050030030050006c852ad-d805-43c3-99d6-93a6a86f507cc5830c26-d503-4496-9142-9a7f188b75488259a51a-a8cf-429a-8620-b1ff4190ca11a07c475c-60f3-4ff9-bff8-2a4f54329a61info:eu-repo/semantics/openAccessreponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALROSA, WILIAN CARVALHO DA.pdfapplication/pdf5138578http://repositorio.ufsm.br/bitstream/1/10616/1/ROSA%2c%20WILIAN%20CARVALHO%20DA.pdfb84a1cdc4fbbcb02094232c6759116d1MD51TEXTROSA, WILIAN CARVALHO DA.pdf.txtROSA, WILIAN CARVALHO DA.pdf.txtExtracted texttext/plain199766http://repositorio.ufsm.br/bitstream/1/10616/2/ROSA%2c%20WILIAN%20CARVALHO%20DA.pdf.txt190a1be077b3bea80e2546ac6f1036a8MD52THUMBNAILROSA, WILIAN CARVALHO DA.pdf.jpgROSA, WILIAN CARVALHO DA.pdf.jpgIM Thumbnailimage/jpeg5206http://repositorio.ufsm.br/bitstream/1/10616/3/ROSA%2c%20WILIAN%20CARVALHO%20DA.pdf.jpg2f8cadb304d5c47f4d1952712aaa76e7MD531/106162017-07-25 12:05:14.68oai:repositorio.ufsm.br:1/10616Repositório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132017-07-25T15:05:14Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
dc.title.alternative.eng.fl_str_mv |
Synthesis of spiro[chromene[4,3-d]Pyrimidines-5,1'-cycloalkane] and 5,6-dihydrobenzo[h]quinazolines trifluoromethyl substituted |
title |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
spellingShingle |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas Rosa, Wilian Carvalho da Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
title_full |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
title_fullStr |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
title_full_unstemmed |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
title_sort |
Síntese de espiro[cromeno[4,3-d]pirimidinas-5,1 -cicloalcano] e 5,6-diidrobenzo[h]quinazolinas trifluormetil substituídas |
author |
Rosa, Wilian Carvalho da |
author_facet |
Rosa, Wilian Carvalho da |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Bonacorso, Helio Gauze |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4788537E0 |
dc.contributor.referee1.fl_str_mv |
Zeni, Gilson Rogério |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4728651J6 |
dc.contributor.referee2.fl_str_mv |
Severo Filho, Wolmar Alípio |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4790001P6 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/0155076624561301 |
dc.contributor.author.fl_str_mv |
Rosa, Wilian Carvalho da |
contributor_str_mv |
Bonacorso, Helio Gauze Zeni, Gilson Rogério Severo Filho, Wolmar Alípio |
dc.subject.por.fl_str_mv |
Química |
topic |
Química CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present dissertation initially describes new methods for the synthesis of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane], as new trifluoromethyl substituted heterocyclic systems. Cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(1-methoxy-3,4-dihydronaphthalen-2-yl)ethanone and five amidines [NH2-(C=NH)R] conducted to the synthesis of a new series of five examples of 2-substituted 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolines in 40-70% yield, where R = 2-substituent = H, methyl, phenyl, NH2 or SCH3. In sequence, a new series of nine unpublished 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidines-5,1'-cycloalkane] were obtained in 73-95% yield from cyclocondensation reactions type [3 + 3] involving 2,2,2-trifluoro-1-(4-methoxyspiro[chromene-2,1'-cycloalkane]-3-yl)ethanones and some amidines. These new spiro-heterocyclic structures have a methyl, phenyl or NH2 substituent attached to the position-2 and a 5-, 6- or 7-membered cycloalkane at the spiroposition-5, simultaneously. Finally, to demonstrate the synthetic utility of the 2-amino substituent attached to the obtained heterocycles, N-derivatization reactions of 4-(trifluoromethyl)-5,6-dihydrobenzo[h]quinazolin-2-amine and 4-(trifluoromethyl)spiro[chromeno[4,3-d]pyrimidine-5,1'-cyclopentan]-2-amines employing 2,5-dimethoxytetrahydrofuran in acetic acid medium (Clauson-Kaas reaction) by two methods are described. The first method followed a two-step reaction procedure (35-55%) and the second an "one pot" method (45-55%). The "one-pot" method was the most advantageous by some experimental aspects. However, both methods allowed an efficient conversion of the 2-amino group into the 2-(1H-pyrrol-1-yl) substituent and the obtainment of four new examples of 2- (1H-pyrrol-yl)-substituted heterocyclic molecules. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-02-23 |
dc.date.accessioned.fl_str_mv |
2017-05-26 |
dc.date.available.fl_str_mv |
2017-05-26 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.citation.fl_str_mv |
ROSA, Wilian Carvalho da. Synthesis of spiro[chromene[4,3-d]Pyrimidines-5,1'-cycloalkane] and 5,6-dihydrobenzo[h]quinazolines trifluoromethyl substituted. 2016. 187 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/10616 |
identifier_str_mv |
ROSA, Wilian Carvalho da. Synthesis of spiro[chromene[4,3-d]Pyrimidines-5,1'-cycloalkane] and 5,6-dihydrobenzo[h]quinazolines trifluoromethyl substituted. 2016. 187 f. Dissertação (Mestrado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2016. |
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http://repositorio.ufsm.br/handle/1/10616 |
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Universidade Federal de Santa Maria |
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UFSM |
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Química |
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Universidade Federal de Santa Maria |
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