Controle estereoquímico na preparação de calcogenetos vinílicos

Detalhes bibliográficos
Autor(a) principal: Santos, Paulo César Silva dos
Data de Publicação: 2004
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Manancial - Repositório Digital da UFSM
Texto Completo: http://repositorio.ufsm.br/handle/1/23856
Resumo: We describe here a quite general method for the synthesis of vinylic chalcogenides by a nucleophilic vinylic substitution. Thus, the treatment of sodium chalcogenolates with (E) and (Z)--bromostyrenes allows the preparation of the desired products in very large scale and using inexpensive reagents. The reaction was observed to occur with total retention of configuration of the starting vinylic halide, and good yields of the products were obtained. The reaction showed to be applicable also to deactivated vinylic halides, as can be seen on Scheme 1. The methodology is based on the cleavage of diaryldichalcogenides with NaBH4 in ethanol. Substitution of ethanol by DMF under heating, followed by addition of the convenient vinylic halides furnishes the desired product ...
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spelling 2022-03-23T15:41:58Z2022-03-23T15:41:58Z2004http://repositorio.ufsm.br/handle/1/23856We describe here a quite general method for the synthesis of vinylic chalcogenides by a nucleophilic vinylic substitution. Thus, the treatment of sodium chalcogenolates with (E) and (Z)--bromostyrenes allows the preparation of the desired products in very large scale and using inexpensive reagents. The reaction was observed to occur with total retention of configuration of the starting vinylic halide, and good yields of the products were obtained. The reaction showed to be applicable also to deactivated vinylic halides, as can be seen on Scheme 1. The methodology is based on the cleavage of diaryldichalcogenides with NaBH4 in ethanol. Substitution of ethanol by DMF under heating, followed by addition of the convenient vinylic halides furnishes the desired product ...Neste trabalho, desenvolvemos uma metodologia para a síntese de sulfetos, selenetos e teluretos através de reação de substituição nucleofílica vinílica. Os teluretos, selenetos e sulfetos vinílicos foram obtidos a partir de reação de substituição nucleofílica vinílica em haletos vinílicos pelos calcogenolatos de sódio correspondente, sendo que a facilidade na obtenção dos reagentes para estas reações, viabiliza a sua utilização em preparações de larga escala. A reação ocorre com total retenção de configuração a partir do haleto vinílico utilizado, sendo obtidos os produtos em bons rendimentos. A metodologia estudada está baseada na clivagem de dicalcogenetos de diarila, reagentes facilmente acessíveis, com hidreto de boro e sódio em etanol, com substituição posterior do solvente etanol por DMF com o auxílio de um Dean Stark para a remoção do solvente etanol do sistema reacional sob aquecimento, seguido pela adição da espécie vinílica adequada fornecendo os correspondentes calcogenetos vinílicos....Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessCalcogenetos vinílicosCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAControle estereoquímico na preparação de calcogenetos vinílicosStereochemical control on the preparation of vinylic chalcogenidesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisSilveira, Claudio da Cruzhttp://lattes.cnpq.br/6152568411858220Lenardão, Eder JoãoAppelt, Helmoz Roseniaimhttp://lattes.cnpq.br/0550543249676037Santos, Paulo César Silva dos1006000000006006006006006003be6a9b9-f9d9-448f-9487-6074331b34a18a02e017-d71e-4152-b3c3-0097a4348babe691b469-6aea-4035-abef-285e61ba7eb54684f279-563c-45a1-a01d-7d0ddd2378cbreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2004_SANTOS_PAULO.pdfDIS_PPGQUIMICA_2004_SANTOS_PAULO.pdfDissertaçãoapplication/pdf12272952http://repositorio.ufsm.br/bitstream/1/23856/1/DIS_PPGQUIMICA_2004_SANTOS_PAULO.pdf1cb6a3781a42936fbf59568beafdaa62MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/23856/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/23856/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD531/238562022-03-23 12:41:59.088oai:repositorio.ufsm.br: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ório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestopendoar:39132022-03-23T15:41:59Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false
dc.title.por.fl_str_mv Controle estereoquímico na preparação de calcogenetos vinílicos
dc.title.alternative.eng.fl_str_mv Stereochemical control on the preparation of vinylic chalcogenides
title Controle estereoquímico na preparação de calcogenetos vinílicos
spellingShingle Controle estereoquímico na preparação de calcogenetos vinílicos
Santos, Paulo César Silva dos
Calcogenetos vinílicos
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Controle estereoquímico na preparação de calcogenetos vinílicos
title_full Controle estereoquímico na preparação de calcogenetos vinílicos
title_fullStr Controle estereoquímico na preparação de calcogenetos vinílicos
title_full_unstemmed Controle estereoquímico na preparação de calcogenetos vinílicos
title_sort Controle estereoquímico na preparação de calcogenetos vinílicos
author Santos, Paulo César Silva dos
author_facet Santos, Paulo César Silva dos
author_role author
dc.contributor.advisor1.fl_str_mv Silveira, Claudio da Cruz
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/6152568411858220
dc.contributor.referee1.fl_str_mv Lenardão, Eder João
dc.contributor.referee2.fl_str_mv Appelt, Helmoz Roseniaim
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/0550543249676037
dc.contributor.author.fl_str_mv Santos, Paulo César Silva dos
contributor_str_mv Silveira, Claudio da Cruz
Lenardão, Eder João
Appelt, Helmoz Roseniaim
dc.subject.por.fl_str_mv Calcogenetos vinílicos
topic Calcogenetos vinílicos
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
dc.subject.cnpq.fl_str_mv CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description We describe here a quite general method for the synthesis of vinylic chalcogenides by a nucleophilic vinylic substitution. Thus, the treatment of sodium chalcogenolates with (E) and (Z)--bromostyrenes allows the preparation of the desired products in very large scale and using inexpensive reagents. The reaction was observed to occur with total retention of configuration of the starting vinylic halide, and good yields of the products were obtained. The reaction showed to be applicable also to deactivated vinylic halides, as can be seen on Scheme 1. The methodology is based on the cleavage of diaryldichalcogenides with NaBH4 in ethanol. Substitution of ethanol by DMF under heating, followed by addition of the convenient vinylic halides furnishes the desired product ...
publishDate 2004
dc.date.issued.fl_str_mv 2004
dc.date.accessioned.fl_str_mv 2022-03-23T15:41:58Z
dc.date.available.fl_str_mv 2022-03-23T15:41:58Z
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url http://repositorio.ufsm.br/handle/1/23856
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http://creativecommons.org/licenses/by-nc-nd/4.0/
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dc.publisher.none.fl_str_mv Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas
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 Brasil
dc.publisher.department.fl_str_mv Química
publisher.none.fl_str_mv Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas
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