Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides
Autor(a) principal: | |
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Data de Publicação: | 1993 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | https://hdl.handle.net/1822/72933 |
Resumo: | A study of the selective cathodic cleavage of one of the alkoxycarbonyl or acyl groups from various imidodicarbonates, acylamides, and diacylamides is reported. The compounds investigated include all 15 possible combinations of the following groups in unsymmetrical N,N-diprotected derivatives of benzylamine: p-nitrobenzyloxycarbonyl, trichloroethyloxycarbonyl, toluene-p-sulfonyl, benzoyl, benzyloxycarbonyl, and tert-butyloxycarbonyl which can all be electrochemically cleavaged, except the last one. Initially the compounds were examined by cyclic voltammetry in order to measure the potentials associated with the cleavage of each group and afterwards they were electrolysed at constant potential in the presence of a proton donor. The following ranges in negative potential were recorded: 1.03-1.13 V [Z(NO2)], 1.8-2.14 V (Troc), 1.75-2.41 V (Tos), 1.88-2.52 V (Bz), and 2.83-2.9 V (Z), thus occasionally revealing a drastic effect of the auxiliary group. In the electrolytic experiments competitive attack by base occasionally led to mixtures of monoacylamides. However, all compounds apart from some of the trichloroethyloxycarbonyl derivatives could be selectively cleaved in 89-100% yields when an appropriate proton donor was used. Tentative explanations are given for the behaviour of the compounds studied and some conclusions are drawn. |
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Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamidesScience & TechnologyA study of the selective cathodic cleavage of one of the alkoxycarbonyl or acyl groups from various imidodicarbonates, acylamides, and diacylamides is reported. The compounds investigated include all 15 possible combinations of the following groups in unsymmetrical N,N-diprotected derivatives of benzylamine: p-nitrobenzyloxycarbonyl, trichloroethyloxycarbonyl, toluene-p-sulfonyl, benzoyl, benzyloxycarbonyl, and tert-butyloxycarbonyl which can all be electrochemically cleavaged, except the last one. Initially the compounds were examined by cyclic voltammetry in order to measure the potentials associated with the cleavage of each group and afterwards they were electrolysed at constant potential in the presence of a proton donor. The following ranges in negative potential were recorded: 1.03-1.13 V [Z(NO2)], 1.8-2.14 V (Troc), 1.75-2.41 V (Tos), 1.88-2.52 V (Bz), and 2.83-2.9 V (Z), thus occasionally revealing a drastic effect of the auxiliary group. In the electrolytic experiments competitive attack by base occasionally led to mixtures of monoacylamides. However, all compounds apart from some of the trichloroethyloxycarbonyl derivatives could be selectively cleaved in 89-100% yields when an appropriate proton donor was used. Tentative explanations are given for the behaviour of the compounds studied and some conclusions are drawn.Royal Society of ChemistryUniversidade do MinhoMaia, Hernâni Lopes SilvaMonteiro, Luís S.Degerbeck, FredrikGrehn, LeifRagnarsson, Ulf1993-031993-03-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/1822/72933engMaia, H. L. S., Monteiro, L. S., Degerbeck, F., Grehn, L., & Ragnarsson, U. (1993). Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides. [10.1039/P29930000495]. Journal of the Chemical Society, Perkin Transactions 2(3), 495-500. doi: 10.1039/p299300004951472-779X10.1039/P29930000495https://pubs.rsc.org/en/Content/ArticleLanding/P2/1993/P29930000495info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2023-07-21T12:44:02Zoai:repositorium.sdum.uminho.pt:1822/72933Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T19:41:39.138645Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
title |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
spellingShingle |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides Maia, Hernâni Lopes Silva Science & Technology |
title_short |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
title_full |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
title_fullStr |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
title_full_unstemmed |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
title_sort |
Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides |
author |
Maia, Hernâni Lopes Silva |
author_facet |
Maia, Hernâni Lopes Silva Monteiro, Luís S. Degerbeck, Fredrik Grehn, Leif Ragnarsson, Ulf |
author_role |
author |
author2 |
Monteiro, Luís S. Degerbeck, Fredrik Grehn, Leif Ragnarsson, Ulf |
author2_role |
author author author author |
dc.contributor.none.fl_str_mv |
Universidade do Minho |
dc.contributor.author.fl_str_mv |
Maia, Hernâni Lopes Silva Monteiro, Luís S. Degerbeck, Fredrik Grehn, Leif Ragnarsson, Ulf |
dc.subject.por.fl_str_mv |
Science & Technology |
topic |
Science & Technology |
description |
A study of the selective cathodic cleavage of one of the alkoxycarbonyl or acyl groups from various imidodicarbonates, acylamides, and diacylamides is reported. The compounds investigated include all 15 possible combinations of the following groups in unsymmetrical N,N-diprotected derivatives of benzylamine: p-nitrobenzyloxycarbonyl, trichloroethyloxycarbonyl, toluene-p-sulfonyl, benzoyl, benzyloxycarbonyl, and tert-butyloxycarbonyl which can all be electrochemically cleavaged, except the last one. Initially the compounds were examined by cyclic voltammetry in order to measure the potentials associated with the cleavage of each group and afterwards they were electrolysed at constant potential in the presence of a proton donor. The following ranges in negative potential were recorded: 1.03-1.13 V [Z(NO2)], 1.8-2.14 V (Troc), 1.75-2.41 V (Tos), 1.88-2.52 V (Bz), and 2.83-2.9 V (Z), thus occasionally revealing a drastic effect of the auxiliary group. In the electrolytic experiments competitive attack by base occasionally led to mixtures of monoacylamides. However, all compounds apart from some of the trichloroethyloxycarbonyl derivatives could be selectively cleaved in 89-100% yields when an appropriate proton donor was used. Tentative explanations are given for the behaviour of the compounds studied and some conclusions are drawn. |
publishDate |
1993 |
dc.date.none.fl_str_mv |
1993-03 1993-03-01T00:00:00Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
https://hdl.handle.net/1822/72933 |
url |
https://hdl.handle.net/1822/72933 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Maia, H. L. S., Monteiro, L. S., Degerbeck, F., Grehn, L., & Ragnarsson, U. (1993). Selective cathodic cleavage of unsymmetrical imidodicarbonates, acylcarbamates and diacylamides. [10.1039/P29930000495]. Journal of the Chemical Society, Perkin Transactions 2(3), 495-500. doi: 10.1039/p29930000495 1472-779X 10.1039/P29930000495 https://pubs.rsc.org/en/Content/ArticleLanding/P2/1993/P29930000495 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Royal Society of Chemistry |
publisher.none.fl_str_mv |
Royal Society of Chemistry |
dc.source.none.fl_str_mv |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799132965731565568 |