Síntese de BIS-1H-pirazóis trialometil substituídos
Autor(a) principal: | |
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Data de Publicação: | 2008 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/4167 |
Resumo: | The present research describes the use of b-alcoxyvinyl trihalomethyl ketones (1,2) [CX3C(O)CHCRR1, where X: Cl, F; R: H, Me, Ph, 4-MePh, 4-MeOPh, 4-FPh, 4- ClPh, 4-BrPh, 4-NO2Ph, 4,4 -Biphenyl, 1-Naphtyl, 2-Furyl, 2- Thienyl; R1: OMe, OEt] in the regioselective synthesis of Oxalyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro- 1H-pyrazoles (6,8), Succinyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro-1Hpyrazoles (10,14), Succinyl-1-(5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole- 1 -(5-trichloromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole (13) e Carbonyl-1,1 -Bis-5- trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole (16), obtained from the cyclocondensation reaction of 1,1,1-trihalo-4-alkoxy-3-alken-2-ones (1,2) and dihydrazide oxallyc, di-hydrazide succinic and carbohydrazide, respectively. For the synthesis of these compounds, ethanol was used as solvent, at temperature of 50-80 oC, in reaction time of 2-16 hours, with yields of 51-91%. The Bis-5-hydroxy-4,5-dihydro-1H-pyrazolines (6,8,10,14,16) were submitted the dehydration reactions carried out in thionyl choride, pyridine, benzene, at temperature of 0-80 oC, giving the aromatic compounds Oxalyl-1,1 -Bis-3-aryl-5-trihalomethyl-1Hpyrazoles (7,9) and Succinil-1,1 -Bis-5-trihalomethyl-1H-pyrazoles (11,15), with yields of 53-78%. Also, were obtained a series of Carbonyl-1,1 -Bis-5-trihalomethyl-1Hpyrazoles (3,5), in direct synthesis, thus, in one pot method, from the vinyl trihalomethyl ketones (1,2) and 1,3-diaminoguanidine hydrochloride, carried out in ethanol/water, reaction time of 4-5 hours, with yields of 62-86%. Finally, 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1-succinilhydrazino-1Hpyrazole (12) and 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole-1- carbohydrazide (18), were chemoselectively synthesized, in mild conditions reactions and using ethanol as solvent , in reaction time of 4 hours, with yields of 44-86%, respectively. The cyclocondensation reaction of the compounds (12,18) using vinyl trihalomethyl ketones (1) with di-hydrazide succinic or carbohydrazide, and in molar ratio of 1:1. The compounds were characterized by spectral and analytical experiments of 1H s and 13C s NMR, X-Ray Difraction, and the purity were demonstrated by elemental analyzes. |
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Síntese de BIS-1H-pirazóis trialometil substituídosSynthesis of trihalomethyl substituted BIS-1H-pyrazolesHeterociclosBis-pirazóisHidrazidasGuanidinasTriclorometiladosTrifluormetiladosCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe present research describes the use of b-alcoxyvinyl trihalomethyl ketones (1,2) [CX3C(O)CHCRR1, where X: Cl, F; R: H, Me, Ph, 4-MePh, 4-MeOPh, 4-FPh, 4- ClPh, 4-BrPh, 4-NO2Ph, 4,4 -Biphenyl, 1-Naphtyl, 2-Furyl, 2- Thienyl; R1: OMe, OEt] in the regioselective synthesis of Oxalyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro- 1H-pyrazoles (6,8), Succinyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro-1Hpyrazoles (10,14), Succinyl-1-(5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole- 1 -(5-trichloromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole (13) e Carbonyl-1,1 -Bis-5- trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole (16), obtained from the cyclocondensation reaction of 1,1,1-trihalo-4-alkoxy-3-alken-2-ones (1,2) and dihydrazide oxallyc, di-hydrazide succinic and carbohydrazide, respectively. For the synthesis of these compounds, ethanol was used as solvent, at temperature of 50-80 oC, in reaction time of 2-16 hours, with yields of 51-91%. The Bis-5-hydroxy-4,5-dihydro-1H-pyrazolines (6,8,10,14,16) were submitted the dehydration reactions carried out in thionyl choride, pyridine, benzene, at temperature of 0-80 oC, giving the aromatic compounds Oxalyl-1,1 -Bis-3-aryl-5-trihalomethyl-1Hpyrazoles (7,9) and Succinil-1,1 -Bis-5-trihalomethyl-1H-pyrazoles (11,15), with yields of 53-78%. Also, were obtained a series of Carbonyl-1,1 -Bis-5-trihalomethyl-1Hpyrazoles (3,5), in direct synthesis, thus, in one pot method, from the vinyl trihalomethyl ketones (1,2) and 1,3-diaminoguanidine hydrochloride, carried out in ethanol/water, reaction time of 4-5 hours, with yields of 62-86%. Finally, 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1-succinilhydrazino-1Hpyrazole (12) and 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole-1- carbohydrazide (18), were chemoselectively synthesized, in mild conditions reactions and using ethanol as solvent , in reaction time of 4 hours, with yields of 44-86%, respectively. The cyclocondensation reaction of the compounds (12,18) using vinyl trihalomethyl ketones (1) with di-hydrazide succinic or carbohydrazide, and in molar ratio of 1:1. The compounds were characterized by spectral and analytical experiments of 1H s and 13C s NMR, X-Ray Difraction, and the purity were demonstrated by elemental analyzes.Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorA presente tese descreve a utilização de �-alcoxivinil trialometil cetonas (1,2)[CX3C(O)CHCRR1, onde X: Cl, F; R: H, Me, Ph, 4-MePh, 4-MeOPh, 4-FPh, 4-ClPh, 4-BrPh, 4-NO2Ph, 4,4 -Bifenil, 1-Naftil, 2-Furil, 2- Tienil; R1: OMe, OEt] na síntese regiosseletiva de Oxalil-1,1 -Bis-5-trialometil-5-hidróxi-4,5-diidro-1H-pirazóis (6,8), Succinil-1,1 -Bis-5-trialometil-5-hidróxi-4,5-diidro-1H-pirazóis (10,14), Succinil-1-(5-trifluormetil-5-hidróxi-4,5-diidro-1H)-pirazol-1 -(5-triclorometil-5-hidróxi-4,5-diidro- 1H)-pirazol (13) e Carbonil-1,1 -Bis-5-trifluormetil-5-hidróxi-4,5-diidro-1H-pirazol (16),obtidos a partir de reações de ciclocondensação entre 1,1,1-trialo-4-alcóxi-3-alquen-2- onas (1,2) e di-hidrazida oxálica, di-hidrazida succínica e carbohidrazida, respectivamente. Para a síntese destes compostos foi utilizado etanol como solvente, a temperatura de 50-80ºC, em tempo reacional de 2-16 horas, com rendimento de 51-91%. As Bis-5-hidróxi-4,5-diidro-1H-pirazolinas (6,8,10,14,16) foram submetidas a condições de desidratração, utilizando metodologia que emprega cloreto de tionila, piridina e benzeno como meio reacional, à temperatura de 0-80 oC, conduzindo a obtenção dos compostos aromatizados Oxalil-1,1 -Bis-3-aril-5-trialometil-1H-pirazóis (7,9) e Succinil-1,1 -Bis-5-trialometil-1H-pirazóis (11,15), com rendimentos de 53-78%. Também, foram obtidos Carbonil-1,1 -Bis-5-trialometil-1H-pirazóis (3,5) a partir da síntese direta, ou seja, em passo reacional único, entre as vinil cetonas trialometiladas (1,2) e cloridrato de 1,3-diaminoguanidina, em etanol/água, em tempo reacional de 4-5 horas, com rendimentos de 62-86%. Finalmente, foram sintetizados por metodologia quimiosseletiva os produtos 5- trifluormetil-5-hidróxi-4,5-diidro-1-succinilhidrazino-1H-pirazol (12) e 5-trifluormetil-5- hidróxi-4,5-diidro-1H-pirazol-1-carbohidrazida (18), em condições reacionais mais brandas e que utilizaram etanol como solvente, em tempo reacional de 4 horas, com rendimentos de 44-86%, respectivamente. As reações de ciclocondensação dos compostos (12,18) empregaram vinil cetonas trifluormetiladas (1) com di-hidrazida succínica ou carbohidrazida e em relação molar de 1:1. Os compostos foram caracterizados por experimentos de RMN de 1H e13C {H}, Difração de Raios-X e sua pureza determinada via Análise Elementar.Universidade Federal de Santa MariaBRQuímicaUFSMPrograma de Pós-Graduação em QuímicaBonacorso, Helio Gauzehttp://lattes.cnpq.br/7275608974248322Zanatta, Nilohttp://lattes.cnpq.br/0719465062354576Martins, Marcos Antonio Pintohttp://lattes.cnpq.br/6457412713967642Rodrigues, Oscar Endrigo Dorneleshttp://lattes.cnpq.br/6536519955416085Severo Filho, Wolmar Alípiohttp://lattes.cnpq.br/1999826579939679Cechinel, Cleber André2017-05-122017-05-122008-10-03info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfapplication/pdfCECHINEL, Cleber André. Synthesis of trihalomethyl substituted BIS-1H-pyrazoles. 2008. 286 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008.http://repositorio.ufsm.br/handle/1/4167porinfo:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2023-04-20T13:05:47Zoai:repositorio.ufsm.br:1/4167Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2023-04-20T13:05:47Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Síntese de BIS-1H-pirazóis trialometil substituídos Synthesis of trihalomethyl substituted BIS-1H-pyrazoles |
title |
Síntese de BIS-1H-pirazóis trialometil substituídos |
spellingShingle |
Síntese de BIS-1H-pirazóis trialometil substituídos Cechinel, Cleber André Heterociclos Bis-pirazóis Hidrazidas Guanidinas Triclorometilados Trifluormetilados CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese de BIS-1H-pirazóis trialometil substituídos |
title_full |
Síntese de BIS-1H-pirazóis trialometil substituídos |
title_fullStr |
Síntese de BIS-1H-pirazóis trialometil substituídos |
title_full_unstemmed |
Síntese de BIS-1H-pirazóis trialometil substituídos |
title_sort |
Síntese de BIS-1H-pirazóis trialometil substituídos |
author |
Cechinel, Cleber André |
author_facet |
Cechinel, Cleber André |
author_role |
author |
dc.contributor.none.fl_str_mv |
Bonacorso, Helio Gauze http://lattes.cnpq.br/7275608974248322 Zanatta, Nilo http://lattes.cnpq.br/0719465062354576 Martins, Marcos Antonio Pinto http://lattes.cnpq.br/6457412713967642 Rodrigues, Oscar Endrigo Dorneles http://lattes.cnpq.br/6536519955416085 Severo Filho, Wolmar Alípio http://lattes.cnpq.br/1999826579939679 |
dc.contributor.author.fl_str_mv |
Cechinel, Cleber André |
dc.subject.por.fl_str_mv |
Heterociclos Bis-pirazóis Hidrazidas Guanidinas Triclorometilados Trifluormetilados CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Heterociclos Bis-pirazóis Hidrazidas Guanidinas Triclorometilados Trifluormetilados CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
The present research describes the use of b-alcoxyvinyl trihalomethyl ketones (1,2) [CX3C(O)CHCRR1, where X: Cl, F; R: H, Me, Ph, 4-MePh, 4-MeOPh, 4-FPh, 4- ClPh, 4-BrPh, 4-NO2Ph, 4,4 -Biphenyl, 1-Naphtyl, 2-Furyl, 2- Thienyl; R1: OMe, OEt] in the regioselective synthesis of Oxalyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro- 1H-pyrazoles (6,8), Succinyl-1,1 -Bis-5-trihalomethyl-5-hydroxy-4,5-dihydro-1Hpyrazoles (10,14), Succinyl-1-(5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole- 1 -(5-trichloromethyl-5-hydroxy-4,5-dihydro-1H)-pyrazole (13) e Carbonyl-1,1 -Bis-5- trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole (16), obtained from the cyclocondensation reaction of 1,1,1-trihalo-4-alkoxy-3-alken-2-ones (1,2) and dihydrazide oxallyc, di-hydrazide succinic and carbohydrazide, respectively. For the synthesis of these compounds, ethanol was used as solvent, at temperature of 50-80 oC, in reaction time of 2-16 hours, with yields of 51-91%. The Bis-5-hydroxy-4,5-dihydro-1H-pyrazolines (6,8,10,14,16) were submitted the dehydration reactions carried out in thionyl choride, pyridine, benzene, at temperature of 0-80 oC, giving the aromatic compounds Oxalyl-1,1 -Bis-3-aryl-5-trihalomethyl-1Hpyrazoles (7,9) and Succinil-1,1 -Bis-5-trihalomethyl-1H-pyrazoles (11,15), with yields of 53-78%. Also, were obtained a series of Carbonyl-1,1 -Bis-5-trihalomethyl-1Hpyrazoles (3,5), in direct synthesis, thus, in one pot method, from the vinyl trihalomethyl ketones (1,2) and 1,3-diaminoguanidine hydrochloride, carried out in ethanol/water, reaction time of 4-5 hours, with yields of 62-86%. Finally, 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1-succinilhydrazino-1Hpyrazole (12) and 5-trifluoromethyl-5-hydroxy-4,5-dihydro-1H-pyrazole-1- carbohydrazide (18), were chemoselectively synthesized, in mild conditions reactions and using ethanol as solvent , in reaction time of 4 hours, with yields of 44-86%, respectively. The cyclocondensation reaction of the compounds (12,18) using vinyl trihalomethyl ketones (1) with di-hydrazide succinic or carbohydrazide, and in molar ratio of 1:1. The compounds were characterized by spectral and analytical experiments of 1H s and 13C s NMR, X-Ray Difraction, and the purity were demonstrated by elemental analyzes. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-10-03 2017-05-12 2017-05-12 |
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.uri.fl_str_mv |
CECHINEL, Cleber André. Synthesis of trihalomethyl substituted BIS-1H-pyrazoles. 2008. 286 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008. http://repositorio.ufsm.br/handle/1/4167 |
identifier_str_mv |
CECHINEL, Cleber André. Synthesis of trihalomethyl substituted BIS-1H-pyrazoles. 2008. 286 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2008. |
url |
http://repositorio.ufsm.br/handle/1/4167 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria BR Química UFSM Programa de Pós-Graduação em Química |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
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1805922052494852096 |