Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes
Autor(a) principal: | |
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Data de Publicação: | 2018 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10400.21/9080 |
Resumo: | Reaction of N-acetylpyrazine-2-carbohydrazide (H2L) with anhydrous Fe(II) or Fe(III) chloride in CH3CN or in MeOH leads to the mononuclear [Fe(kNN’O-HL)Cl2] (1) or binuclear [Fe(kNN’O-HL) Cl(μ-OMe)]2 (2) Fe(III) complex, respectively. These complexes are characterized by elemental analysis, ESI-MS, IR spectroscopy, single-crystal X-ray crystallography, electrochemical techniques and DFT calculations. The theoretical calculations indicate that the three single-electron sequential reductions of 1 are centred at the metal, at the pyrazine group and at both, respectively. The catalytic activity of 1 and 2 was screened towards Friedel-Crafts benzoylation and acylation of m-xylene. The effects of reaction parameters, such as catalyst amount, reaction time and temperature, were studied and, under optimal conditions, 96% yield of 2,4-dimethylbenzophenone and 20% yield of 2,4-dimethylacetophenone were obtained, respectively. Complex 1 exhibited the highest activity in both reactions. The structural and electrochemical properties were supported by theoretical calculations and the importance of the Lewis acid character of the catalyst in the promotion of this catalytic reaction is discussed. |
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Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexesBenzoylationFe(III) complexesFriedel-CraftsReação de benzoilaçãoComplexos de ferroReaction of N-acetylpyrazine-2-carbohydrazide (H2L) with anhydrous Fe(II) or Fe(III) chloride in CH3CN or in MeOH leads to the mononuclear [Fe(kNN’O-HL)Cl2] (1) or binuclear [Fe(kNN’O-HL) Cl(μ-OMe)]2 (2) Fe(III) complex, respectively. These complexes are characterized by elemental analysis, ESI-MS, IR spectroscopy, single-crystal X-ray crystallography, electrochemical techniques and DFT calculations. The theoretical calculations indicate that the three single-electron sequential reductions of 1 are centred at the metal, at the pyrazine group and at both, respectively. The catalytic activity of 1 and 2 was screened towards Friedel-Crafts benzoylation and acylation of m-xylene. The effects of reaction parameters, such as catalyst amount, reaction time and temperature, were studied and, under optimal conditions, 96% yield of 2,4-dimethylbenzophenone and 20% yield of 2,4-dimethylacetophenone were obtained, respectively. Complex 1 exhibited the highest activity in both reactions. The structural and electrochemical properties were supported by theoretical calculations and the importance of the Lewis acid character of the catalyst in the promotion of this catalytic reaction is discussed.Wiley-VCH VerlagRCIPLRoy Barman, TannisthaSutradhar, ManasAlegria, ElisabeteGuedes Da Silva, M. Fátima C.Kuznetsov, Maxim L.Pombeiro, Armando2018-11-23T13:41:25Z2018-07-312018-07-31T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/9080engBARMAN, Tannistha Roy; [et al] – Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes. Chemistry Select. ISSN 2365-6549. Vol. 3, N.º 28 (2018), pp. 8349-83552365-6549https://doi.org/10.1002/slct.201801656metadata only accessinfo: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:RCAAP2023-08-03T09:57:21Zoai:repositorio.ipl.pt:10400.21/9080Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:17:43.622614Repositório 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 |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
title |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
spellingShingle |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes Roy Barman, Tannistha Benzoylation Fe(III) complexes Friedel-Crafts Reação de benzoilação Complexos de ferro |
title_short |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
title_full |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
title_fullStr |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
title_full_unstemmed |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
title_sort |
Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes |
author |
Roy Barman, Tannistha |
author_facet |
Roy Barman, Tannistha Sutradhar, Manas Alegria, Elisabete Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Pombeiro, Armando |
author_role |
author |
author2 |
Sutradhar, Manas Alegria, Elisabete Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Pombeiro, Armando |
author2_role |
author author author author author |
dc.contributor.none.fl_str_mv |
RCIPL |
dc.contributor.author.fl_str_mv |
Roy Barman, Tannistha Sutradhar, Manas Alegria, Elisabete Guedes Da Silva, M. Fátima C. Kuznetsov, Maxim L. Pombeiro, Armando |
dc.subject.por.fl_str_mv |
Benzoylation Fe(III) complexes Friedel-Crafts Reação de benzoilação Complexos de ferro |
topic |
Benzoylation Fe(III) complexes Friedel-Crafts Reação de benzoilação Complexos de ferro |
description |
Reaction of N-acetylpyrazine-2-carbohydrazide (H2L) with anhydrous Fe(II) or Fe(III) chloride in CH3CN or in MeOH leads to the mononuclear [Fe(kNN’O-HL)Cl2] (1) or binuclear [Fe(kNN’O-HL) Cl(μ-OMe)]2 (2) Fe(III) complex, respectively. These complexes are characterized by elemental analysis, ESI-MS, IR spectroscopy, single-crystal X-ray crystallography, electrochemical techniques and DFT calculations. The theoretical calculations indicate that the three single-electron sequential reductions of 1 are centred at the metal, at the pyrazine group and at both, respectively. The catalytic activity of 1 and 2 was screened towards Friedel-Crafts benzoylation and acylation of m-xylene. The effects of reaction parameters, such as catalyst amount, reaction time and temperature, were studied and, under optimal conditions, 96% yield of 2,4-dimethylbenzophenone and 20% yield of 2,4-dimethylacetophenone were obtained, respectively. Complex 1 exhibited the highest activity in both reactions. The structural and electrochemical properties were supported by theoretical calculations and the importance of the Lewis acid character of the catalyst in the promotion of this catalytic reaction is discussed. |
publishDate |
2018 |
dc.date.none.fl_str_mv |
2018-11-23T13:41:25Z 2018-07-31 2018-07-31T00:00:00Z |
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 |
http://hdl.handle.net/10400.21/9080 |
url |
http://hdl.handle.net/10400.21/9080 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
BARMAN, Tannistha Roy; [et al] – Efficient solvent-free friedel-crafts benzoylation and acylation of m-xylene catalyzed by N-acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes. Chemistry Select. ISSN 2365-6549. Vol. 3, N.º 28 (2018), pp. 8349-8355 2365-6549 https://doi.org/10.1002/slct.201801656 |
dc.rights.driver.fl_str_mv |
metadata only access info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
metadata only access |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Wiley-VCH Verlag |
publisher.none.fl_str_mv |
Wiley-VCH Verlag |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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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 |
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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) |
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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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