Efficient solvent-free friedel-crafts benzoylation and acylation of m-Xylene catalyzed by N-Acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexes

Detalhes bibliográficos
Autor(a) principal: Roy Barman, Tannistha
Data de Publicação: 2018
Outros Autores: Sutradhar, Manas, Alegria, Elisabete, Guedes Da Silva, M. Fátima C., Kuznetsov, Maxim L., Pombeiro, Armando
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10400.21/11578
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(kappa NN'O-HL)Cl-2] (1) or binuclear [Fe(kNN'O-HL) Cl(mu-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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spelling Efficient solvent-free friedel-crafts benzoylation and acylation of m-Xylene catalyzed by N-Acetylpyrazine-2-carbohydrazide-Fe(III)-chloro complexesBenzoylationFe(III) complexesFriedel-CraftsSolvent free processX-ray structureReaction of N-acetylpyrazine-2-carbohydrazide (H2L) with anhydrous Fe(II) or Fe(III) chloride in CH3CN or in MeOH leads to the mononuclear [Fe(kappa NN'O-HL)Cl-2] (1) or binuclear [Fe(kNN'O-HL) Cl(mu-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, Armando2020-05-04T16:56:15Z2018-07-312018-07-31T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10400.21/11578engBARMAN, 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. ChemistrySelect. ISSN 2365-6549. Vol. 3, N.º 28 (2018), pp. 8349-83552365-654910.1002/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:RCAAP2023-08-03T10:02:59Zoai:repositorio.ipl.pt:10400.21/11578Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:19:48.520554Repositório 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
Solvent free process
X-ray structure
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
Solvent free process
X-ray structure
topic Benzoylation
Fe(III) complexes
Friedel-Crafts
Solvent free process
X-ray structure
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(kappa NN'O-HL)Cl-2] (1) or binuclear [Fe(kNN'O-HL) Cl(mu-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 2018-07-31
2018-07-31T00:00:00Z
2020-05-04T16:56:15Z
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/10400.21/11578
url http://hdl.handle.net/10400.21/11578
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. ChemistrySelect. ISSN 2365-6549. Vol. 3, N.º 28 (2018), pp. 8349-8355
2365-6549
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)
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