Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos
Ano de defesa: | 2014 |
---|---|
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/1/4287 |
Resumo: | This work presents the synthesis of three series of trifluoromethylated heterocycles by using ultrasound irradiation, nomely pyrazolo[1,5-a]pyrimidines, 2,4- difluorophenylpyrazoles and pentafluorophenylpyrazoles. The reactions were performed between trifluoromethylated enones ([CF3C(O)CH=C(R)(OMe], where R = Me, Bu, i-Bu, Ph, 4-MeC6H4, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-IC6H4, thien-2-yl, naphthyl and biphenyl) with three different nucleophiles, nomely (3)(5)-amine-(5)(3)- methylpyrazole, 2,4-difluorophenylhydrazine hydrochloride and pentafluorophenylhydrazine. The trifluoromethylated pyrazolo[1,5-a]pyrimidines were obtained within 5 minutes, giving yields of 61-98 %. The series of 2,4- difluorophenylpyrazoles was obtained in good yields (54-85 %) within 15 minutes by acidifying the reaction medium with PTSA. In the case of the pentafluorophenylpyrazoles, two steps were needed: Firtly the respective 4,5- dihydropentafluorophenylpyrazoles were synthesised and then subsequently submitted to dehydration reactions using PTSA for 15 minutes, giving yields of 54-81 %. The synthesized compounds were identified by 1H and 13C, and by 19F NMR spectroscopy in the some case, mass spectrometry and X-ray diffraction. In some cases homo/heteronuclear spatial interactions involving fluorine atoms have been useful for confirming the identity of the obtained isomer. Another part of this tesis was the synthesis of four mechanically interlocked molecules. Two [2]rotaxanes carrying an ester group in the macrocycle unity were synthesized by using two threads (fumaramide and succinamide derivatives). Once synthesized these [2]rotaxanes were submmited to hydrolysis reactions to give [2]rotaxanes with acid carboxilic group. These macromolecules were synthesized aiming at the formation of MOFs (metal organic frameworks). The synthesis of this compound was carried out by using copper (II) and [2]rotaxane derivative fumaramide. This product was identified by X-ray diffractometry. |
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2017-05-182017-05-182014-02-14MARZARI, Mara Regina Bonini. Synthesis of pyrazolo[1,5-a]pyrimidines and fluorophenylpyrazoles trifluoromethylated in ultrasound and synthesis and aplication of [2]rotaxanes. 2014. 353 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2014.http://repositorio.ufsm.br/handle/1/4287This work presents the synthesis of three series of trifluoromethylated heterocycles by using ultrasound irradiation, nomely pyrazolo[1,5-a]pyrimidines, 2,4- difluorophenylpyrazoles and pentafluorophenylpyrazoles. The reactions were performed between trifluoromethylated enones ([CF3C(O)CH=C(R)(OMe], where R = Me, Bu, i-Bu, Ph, 4-MeC6H4, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-IC6H4, thien-2-yl, naphthyl and biphenyl) with three different nucleophiles, nomely (3)(5)-amine-(5)(3)- methylpyrazole, 2,4-difluorophenylhydrazine hydrochloride and pentafluorophenylhydrazine. The trifluoromethylated pyrazolo[1,5-a]pyrimidines were obtained within 5 minutes, giving yields of 61-98 %. The series of 2,4- difluorophenylpyrazoles was obtained in good yields (54-85 %) within 15 minutes by acidifying the reaction medium with PTSA. In the case of the pentafluorophenylpyrazoles, two steps were needed: Firtly the respective 4,5- dihydropentafluorophenylpyrazoles were synthesised and then subsequently submitted to dehydration reactions using PTSA for 15 minutes, giving yields of 54-81 %. The synthesized compounds were identified by 1H and 13C, and by 19F NMR spectroscopy in the some case, mass spectrometry and X-ray diffraction. In some cases homo/heteronuclear spatial interactions involving fluorine atoms have been useful for confirming the identity of the obtained isomer. Another part of this tesis was the synthesis of four mechanically interlocked molecules. Two [2]rotaxanes carrying an ester group in the macrocycle unity were synthesized by using two threads (fumaramide and succinamide derivatives). Once synthesized these [2]rotaxanes were submmited to hydrolysis reactions to give [2]rotaxanes with acid carboxilic group. These macromolecules were synthesized aiming at the formation of MOFs (metal organic frameworks). The synthesis of this compound was carried out by using copper (II) and [2]rotaxane derivative fumaramide. This product was identified by X-ray diffractometry.Este trabalho apresenta a síntese de três séries de heterociclos trifluorometilados, utilizando irradiação de ultrassom (pirazolo[1,5-a]pirimidinas, 2,4-difluorofenilpirazóis e pentafluorofenilpirazóis). As reações foram realizadas entre enonas trifluorometiladas ([CF3C(O)CH=C(R)(OMe], onde R = Me, Bu, i-Bu, Ph, 4-Me-C6H4, 4-F-C6H4, 4-Cl-C6H4, 4-Br-C6H4, 4-I-C6H4, tien-2-il, bifen-2-il e naftil) e três dinucleófilos diferentes 3-amino-5-metilpirazol, cloridrato de 2,4-difluorofenilhidrazina e pentafluorofenilhidrazina. As pirazolo[1,5-a]pirimidinas trifluorometiladas foram obtidas em 5 minutos de reação com rendimentos de 61-98 %. A série de 2,4- difluorofenilpirazóis foi obtida, acidificando-se o meio de reação com APTS em 15 minutos de reação, e obtendo-se bons rendimentos (54-85 %) no processo. No caso dos pentafluorofenilpirazóis, foram necessárias duas etapas de reação: a primeira a síntese de 4,5-di-idropentafluorofenilpirazóis, e seguida de posterior reação de desidratação utilizando APTS em 15 minutos de reação, obtendo-se produtos com rendimentos de 54-81 %. Após a síntese desses compostos, os mesmos foram identificados por técnicas de RMN de 1H e 13C e de 19F, em alguns casos, espectrometria de massas e difratometria de raios-X. Em alguns casos, através de RMN, foi possível observar interações espaciais do tipo homo/heteronuclear envolvendo átomos de flúor, úteis na confirmação do isômero obtido. Em outra etapa deste trabalho foi desenvolvida a síntese de quatro moléculas mecanicamente entrelaçadas. Foram sintetizados dois [2]rotaxanos com grupamento éster no macrociclo, utilizando dois filamentos lineares (derivados da fumaramida de succinamida). Após a síntese desses [2]rotaxanos, foi realizada a reação de hidrólise dos grupamentos ésteres do macrociclo em grupamento ácidos. Essas macromoléculas foram sintetizadas visando à formação dos MOFs (Redes de metais orgânicas). A síntese desse composto foi realizada utilizando cobre (II) e o [2]rotaxano derivado da fumaramida. Esse produto foi identificado através de difratometria de Raios-X.Conselho Nacional de Desenvolvimento Científico e Tecnológicoapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaPirazolo[1,5-a]pirimidinas2,4-difluorofenilpirazóisPentafluorofenilpirazóisUltrassomInterações espaciais[2]rotaxanos MOFsPyrazolo[1,5-a]pyrimidine2,4-difluorophenylpyrazolesPentafluorophenylpyrazolesUltrasoundSpatial interactions[2]rotaxanesMOFsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICASíntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanosSynthesis of pyrazolo[1,5-a]pyrimidines and fluorophenylpyrazoles trifluoromethylated in ultrasound and synthesis and aplication of [2]rotaxanesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisMartins, Marcos Antonio Pintohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4783192P3Resende, Jarbas Magalhãeshttp://lattes.cnpq.br/4995867883627482Fantinel, Leonardohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9Mostardeiro, Marco Aureliohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785681E6Cunico Filho, Wilson Joãohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760083P2http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4256015U6Marzari, Mara Regina Bonini100600000000400300300300300300300c28419d9-6027-4f9c-acd2-76e8067a85d1a1a73847-5df2-4a80-b093-547a5adf29ed69b1a367-c945-49b7-9f5f-e5d128197da7079f4612-cd36-4354-af6f-25f7736dccd21ec253ee-25dd-4b17-801e-c4bf7312a9d8c5ba3c61-bebb-4e91-b7bf-8de1ac69f15finfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALMARZARI, MARA REGINA BONINI.pdfapplication/pdf14244005http://repositorio.ufsm.br/bitstream/1/4287/1/MARZARI%2c%20MARA%20REGINA%20BONINI.pdfe9e6d72a5310e08e9ba9e188df3abfeeMD51TEXTMARZARI, MARA REGINA BONINI.pdf.txtMARZARI, MARA REGINA BONINI.pdf.txtExtracted texttext/plain336000http://repositorio.ufsm.br/bitstream/1/4287/2/MARZARI%2c%20MARA%20REGINA%20BONINI.pdf.txt5bd886a14bba3a36d6df6106a10e1196MD52THUMBNAILMARZARI, MARA REGINA BONINI.pdf.jpgMARZARI, MARA REGINA BONINI.pdf.jpgIM Thumbnailimage/jpeg5160http://repositorio.ufsm.br/bitstream/1/4287/3/MARZARI%2c%20MARA%20REGINA%20BONINI.pdf.jpgf1328cbfcf694489492f1831e37333e5MD531/42872017-07-25 11:05:10.727oai:repositorio.ufsm.br:1/4287Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2017-07-25T14:05:10Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
dc.title.alternative.eng.fl_str_mv |
Synthesis of pyrazolo[1,5-a]pyrimidines and fluorophenylpyrazoles trifluoromethylated in ultrasound and synthesis and aplication of [2]rotaxanes |
title |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
spellingShingle |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos Marzari, Mara Regina Bonini Pirazolo[1,5-a]pirimidinas 2,4-difluorofenilpirazóis Pentafluorofenilpirazóis Ultrassom Interações espaciais [2]rotaxanos MOFs Pyrazolo[1,5-a]pyrimidine 2,4-difluorophenylpyrazoles Pentafluorophenylpyrazoles Ultrasound Spatial interactions [2]rotaxanes MOFs CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
title_full |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
title_fullStr |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
title_full_unstemmed |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
title_sort |
Síntese de pirazolo[1,5-a]pirimidinas e fluorfenilpirazóis trifluormetilados em ultrassom e síntese e aplicação de [2]rotaxanos |
author |
Marzari, Mara Regina Bonini |
author_facet |
Marzari, Mara Regina Bonini |
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 |
Resende, Jarbas Magalhães |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/4995867883627482 |
dc.contributor.referee2.fl_str_mv |
Fantinel, Leonardo |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4777461U9 |
dc.contributor.referee3.fl_str_mv |
Mostardeiro, Marco Aurelio |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4785681E6 |
dc.contributor.referee4.fl_str_mv |
Cunico Filho, Wilson João |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4760083P2 |
dc.contributor.authorLattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4256015U6 |
dc.contributor.author.fl_str_mv |
Marzari, Mara Regina Bonini |
contributor_str_mv |
Martins, Marcos Antonio Pinto Resende, Jarbas Magalhães Fantinel, Leonardo Mostardeiro, Marco Aurelio Cunico Filho, Wilson João |
dc.subject.por.fl_str_mv |
Pirazolo[1,5-a]pirimidinas 2,4-difluorofenilpirazóis Pentafluorofenilpirazóis Ultrassom Interações espaciais [2]rotaxanos MOFs |
topic |
Pirazolo[1,5-a]pirimidinas 2,4-difluorofenilpirazóis Pentafluorofenilpirazóis Ultrassom Interações espaciais [2]rotaxanos MOFs Pyrazolo[1,5-a]pyrimidine 2,4-difluorophenylpyrazoles Pentafluorophenylpyrazoles Ultrasound Spatial interactions [2]rotaxanes MOFs CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Pyrazolo[1,5-a]pyrimidine 2,4-difluorophenylpyrazoles Pentafluorophenylpyrazoles Ultrasound Spatial interactions [2]rotaxanes MOFs |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the synthesis of three series of trifluoromethylated heterocycles by using ultrasound irradiation, nomely pyrazolo[1,5-a]pyrimidines, 2,4- difluorophenylpyrazoles and pentafluorophenylpyrazoles. The reactions were performed between trifluoromethylated enones ([CF3C(O)CH=C(R)(OMe], where R = Me, Bu, i-Bu, Ph, 4-MeC6H4, 4-FC6H4, 4-ClC6H4, 4-BrC6H4, 4-IC6H4, thien-2-yl, naphthyl and biphenyl) with three different nucleophiles, nomely (3)(5)-amine-(5)(3)- methylpyrazole, 2,4-difluorophenylhydrazine hydrochloride and pentafluorophenylhydrazine. The trifluoromethylated pyrazolo[1,5-a]pyrimidines were obtained within 5 minutes, giving yields of 61-98 %. The series of 2,4- difluorophenylpyrazoles was obtained in good yields (54-85 %) within 15 minutes by acidifying the reaction medium with PTSA. In the case of the pentafluorophenylpyrazoles, two steps were needed: Firtly the respective 4,5- dihydropentafluorophenylpyrazoles were synthesised and then subsequently submitted to dehydration reactions using PTSA for 15 minutes, giving yields of 54-81 %. The synthesized compounds were identified by 1H and 13C, and by 19F NMR spectroscopy in the some case, mass spectrometry and X-ray diffraction. In some cases homo/heteronuclear spatial interactions involving fluorine atoms have been useful for confirming the identity of the obtained isomer. Another part of this tesis was the synthesis of four mechanically interlocked molecules. Two [2]rotaxanes carrying an ester group in the macrocycle unity were synthesized by using two threads (fumaramide and succinamide derivatives). Once synthesized these [2]rotaxanes were submmited to hydrolysis reactions to give [2]rotaxanes with acid carboxilic group. These macromolecules were synthesized aiming at the formation of MOFs (metal organic frameworks). The synthesis of this compound was carried out by using copper (II) and [2]rotaxane derivative fumaramide. This product was identified by X-ray diffractometry. |
publishDate |
2014 |
dc.date.issued.fl_str_mv |
2014-02-14 |
dc.date.accessioned.fl_str_mv |
2017-05-18 |
dc.date.available.fl_str_mv |
2017-05-18 |
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 |
MARZARI, Mara Regina Bonini. Synthesis of pyrazolo[1,5-a]pyrimidines and fluorophenylpyrazoles trifluoromethylated in ultrasound and synthesis and aplication of [2]rotaxanes. 2014. 353 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2014. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4287 |
identifier_str_mv |
MARZARI, Mara Regina Bonini. Synthesis of pyrazolo[1,5-a]pyrimidines and fluorophenylpyrazoles trifluoromethylated in ultrasound and synthesis and aplication of [2]rotaxanes. 2014. 353 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2014. |
url |
http://repositorio.ufsm.br/handle/1/4287 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
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BR |
dc.publisher.department.fl_str_mv |
Química |
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Universidade Federal de Santa Maria |
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