Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions
Autor(a) principal: | |
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Data de Publicação: | 2010 |
Outros Autores: | , , |
Tipo de documento: | Artigo de conferência |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UFMS |
Texto Completo: | https://repositorio.ufms.br/handle/123456789/5305 |
Resumo: | Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3) or 2,3- diacetylene-1,4-naphthoquinone (4) it was possible to obtain triazole derivatives (naphthoquinonic). This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1). First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98%) by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62%) from compound 1, along with ethanolic solution (reflux) and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b) by 1,3-dipolar cycloaddition, involving compound (3) and terminal acetylenes (phenylacetylene, a) and glycoside (b) using Cu(OAc)2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5) it was possible to synthesize (6), catalyzed by Pd(PPh3)2Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3) and alkynes (a, yield 23% and b, yield 30%) were conducted using the solvent system, (1:1) terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc)2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65%) and phenylacetylene was prepared using the solvent mixture (2:1) DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh3)2Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C). Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings. |
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2022-10-24T13:47:17Z2022-10-24T13:47:17Z2010-031984-6428https://repositorio.ufms.br/handle/123456789/5305Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3) or 2,3- diacetylene-1,4-naphthoquinone (4) it was possible to obtain triazole derivatives (naphthoquinonic). This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1). First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98%) by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62%) from compound 1, along with ethanolic solution (reflux) and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b) by 1,3-dipolar cycloaddition, involving compound (3) and terminal acetylenes (phenylacetylene, a) and glycoside (b) using Cu(OAc)2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5) it was possible to synthesize (6), catalyzed by Pd(PPh3)2Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3) and alkynes (a, yield 23% and b, yield 30%) were conducted using the solvent system, (1:1) terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc)2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65%) and phenylacetylene was prepared using the solvent mixture (2:1) DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh3)2Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C). Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings.engFundação Universidade Federal de Mato Grosso do SulUFMSBrasilOrbital: The Electronic Journal of ChemistryAttribution-NonCommercial-NoDerivs 3.0 Brazilhttp://creativecommons.org/licenses/by-nc-nd/3.0/br/info:eu-repo/semantics/openAccessCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICANaftoquinonasReação de CicloadiçãoReações QuímicasCycloaddition ReactionNaphthoquinonesChemical ReactionsSynthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactionsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/conferenceObject2Suppl. 1Nascimento, Wilson Silva doSilva, Mauro Gomes daOliveira, Ronaldo Nascimento deCâmara, Celso Amorimreponame:Repositório Institucional da UFMSinstname:Universidade Federal de Mato Grosso do Sul (UFMS)instacron:UFMSLICENSElicense.txtlicense.txttext/plain; charset=utf-82031https://repositorio.ufms.br/bitstream/123456789/5305/3/license.txt9671aa5ac42cb06edaf75013367dfe04MD53CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8811https://repositorio.ufms.br/bitstream/123456789/5305/2/license_rdfe39d27027a6cc9cb039ad269a5db8e34MD52ORIGINALSynthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions.pdfSynthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions.pdfapplication/pdf417016https://repositorio.ufms.br/bitstream/123456789/5305/1/Synthesis%20of%201%2c4-naphthoquinone%20derivatives%20using%201%2c3-dipolar%20cycloaddition%20and%20Sonogashira%20reactions.pdf0a6788f5f5ae9359899738d4fca8c3bdMD51123456789/53052022-10-24 09:47:58.265oai:repositorio.ufms.br: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ório InstitucionalPUBhttps://repositorio.ufms.br/oai/requestri.prograd@ufms.bropendoar:21242022-10-24T13:47:58Repositório Institucional da UFMS - Universidade Federal de Mato Grosso do Sul (UFMS)false |
dc.title.pt_BR.fl_str_mv |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
title |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
spellingShingle |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions Nascimento, Wilson Silva do CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA Naftoquinonas Reação de Cicloadição Reações Químicas Cycloaddition Reaction Naphthoquinones Chemical Reactions |
title_short |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
title_full |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
title_fullStr |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
title_full_unstemmed |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
title_sort |
Synthesis of 1,4-naphthoquinone derivatives using 1,3-dipolar cycloaddition and Sonogashira reactions |
author |
Nascimento, Wilson Silva do |
author_facet |
Nascimento, Wilson Silva do Silva, Mauro Gomes da Oliveira, Ronaldo Nascimento de Câmara, Celso Amorim |
author_role |
author |
author2 |
Silva, Mauro Gomes da Oliveira, Ronaldo Nascimento de Câmara, Celso Amorim |
author2_role |
author author author |
dc.contributor.author.fl_str_mv |
Nascimento, Wilson Silva do Silva, Mauro Gomes da Oliveira, Ronaldo Nascimento de Câmara, Celso Amorim |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA Naftoquinonas Reação de Cicloadição Reações Químicas Cycloaddition Reaction Naphthoquinones Chemical Reactions |
dc.subject.por.fl_str_mv |
Naftoquinonas Reação de Cicloadição Reações Químicas Cycloaddition Reaction Naphthoquinones Chemical Reactions |
description |
Naphthoquinones are known according to their important bio-activities, such as their antitumoral and topoisomerase inhibition properties. From 2-azido (3) or 2,3- diacetylene-1,4-naphthoquinone (4) it was possible to obtain triazole derivatives (naphthoquinonic). This work describes the synthesis of two novel molecules, with triazole groups linked to 1,4-naphthoquinone using the 1,3-dipolar cycloaddition and Sonogashira reactions. The synthetic strategy followed two routes (Scheme 1). First, we synthesized the 2-bromo-1,4-naphthoquinone (2, yield 98%) by using Br2 and CH3CO2H, and then used it to obtain 2-azido-1,4-naphthoquinone (3, yield 62%) from compound 1, along with ethanolic solution (reflux) and NaN3. Finally, we prepared 1,2,3-triazole compounds (4a, b) by 1,3-dipolar cycloaddition, involving compound (3) and terminal acetylenes (phenylacetylene, a) and glycoside (b) using Cu(OAc)2 and ascorbate, under argon atmosphere. During the second step, 2,3-dibromo-1,4-naphthoquinone was prepared using Br2/CH2Cl2 at room temperature. From compound (5) it was possible to synthesize (6), catalyzed by Pd(PPh3)2Cl2/CuI/Et3N, under argon atmosphere, in 40% yield. The 1,3-dipolar cycloaddition reactions involving 2-azido-1,4-naphthoquinone (3) and alkynes (a, yield 23% and b, yield 30%) were conducted using the solvent system, (1:1) terc-BuOH/H2O/r.t/ 20 mol% of Cu(OAc)2 and sodium ascorbate, under stirring during 24 hours. The reaction involving 2,3-dibromo-1,4-naphthoquinone (5, yield 65%) and phenylacetylene was prepared using the solvent mixture (2:1) DMSO/CHCl3 and catalytic amount of CuI/Pd(PPh3)2Cl2. The final products were characterized by elemental analysis and spectrometric techniques (IR, NMR 1H and 13C). Two novel triazole compounds were synthesized from naphthoquinones by 1,3-dipolar cycloaddition from suitable 1,4-naphthoquinones obtained by Sonogashira couplings. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-03 |
dc.date.accessioned.fl_str_mv |
2022-10-24T13:47:17Z |
dc.date.available.fl_str_mv |
2022-10-24T13:47:17Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/conferenceObject |
format |
conferenceObject |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufms.br/handle/123456789/5305 |
dc.identifier.issn.pt_BR.fl_str_mv |
1984-6428 |
identifier_str_mv |
1984-6428 |
url |
https://repositorio.ufms.br/handle/123456789/5305 |
dc.language.iso.fl_str_mv |
eng |
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eng |
dc.relation.ispartof.pt_BR.fl_str_mv |
Orbital: The Electronic Journal of Chemistry |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ info:eu-repo/semantics/openAccess |
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Attribution-NonCommercial-NoDerivs 3.0 Brazil http://creativecommons.org/licenses/by-nc-nd/3.0/br/ |
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openAccess |
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Fundação Universidade Federal de Mato Grosso do Sul |
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UFMS |
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Brasil |
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Fundação Universidade Federal de Mato Grosso do Sul |
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UFMS |
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