The effects of substituents and solvents on the conformation of benzophenones

Autores
Mantas, Athena; Blanco, Sonia Encarnacion; Ferretti, Ferdinando Hector
Año de publicación
2004
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Motivation. Natural and synthetic benzophenones are compounds of great scientific and applied interest due to the varied biological and physicochemical properties that they posses. As part of a program aimed at investigating new physicochemical properties of substituted benzophenones, we carry out a study on the influence of the substituents and solvents upon the molecular conformations of these compounds. In the future, we expect to propose relationships between the molecular structural parameters with diverse experimental properties of the compounds that are currently being determined in our laboratory. Method. The HF/6–31G(d) and B3LYP/6–31G(d) methods were used for calculations. Onsager’s and Tomasi’s models were used to analyze the solvent effects on the nine benzophenones studied. Results. A conformational equilibrium was proposed between the two conformers of benzophenones with the greatest thermodynamic stability. The total energies, torsional angles, dipole moments, structural and reactivity molecular parameters, and conformational equilibrium constants were calculated in vacuum, ethanol, methanol and water. The calculated magnitudes were correlated with Hammett’s substituent constants and parameters of solvating solvents. Conclusions. The benzophenones investigated have non–planar structures. Very good linear relationships between the molecular dihedral angles and Hammett’s p–substituent constants were obtained. Electron–donating substituents increase the planarity of the substituted benzoyl group that involves phenyl ring A of the molecules, as well as the folding of phenyl ring B. The conformational equilibrium constants of o–hydroxy–benzophenones ranged approximately between 10–7–10–6. On the other hand, it was concluded that greater hydrogen–bond donor capability of a solvent increases the polarization of the compounds and consequently, increases their dipole moments. It was further concluded that the electron–donating groups increase the strength of the intramolecular hydrogen bond and that in the solvents used the o–hydroxy–benzophenones possess an important intramolecular hydrogen bond of the moderate class
Fil: Mantas, Athena. University of Toronto; Canadá
Fil: Blanco, Sonia Encarnacion. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Ferretti, Ferdinando Hector. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; Argentina
Materia
Substituted benzophenones
Effects of substituents and solvents
Conformational equilibrium
Hydrogen bonding
Ab initio and DFT methods
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/138375

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spelling The effects of substituents and solvents on the conformation of benzophenonesMantas, AthenaBlanco, Sonia EncarnacionFerretti, Ferdinando HectorSubstituted benzophenonesEffects of substituents and solventsConformational equilibriumHydrogen bondingAb initio and DFT methodshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Motivation. Natural and synthetic benzophenones are compounds of great scientific and applied interest due to the varied biological and physicochemical properties that they posses. As part of a program aimed at investigating new physicochemical properties of substituted benzophenones, we carry out a study on the influence of the substituents and solvents upon the molecular conformations of these compounds. In the future, we expect to propose relationships between the molecular structural parameters with diverse experimental properties of the compounds that are currently being determined in our laboratory. Method. The HF/6–31G(d) and B3LYP/6–31G(d) methods were used for calculations. Onsager’s and Tomasi’s models were used to analyze the solvent effects on the nine benzophenones studied. Results. A conformational equilibrium was proposed between the two conformers of benzophenones with the greatest thermodynamic stability. The total energies, torsional angles, dipole moments, structural and reactivity molecular parameters, and conformational equilibrium constants were calculated in vacuum, ethanol, methanol and water. The calculated magnitudes were correlated with Hammett’s substituent constants and parameters of solvating solvents. Conclusions. The benzophenones investigated have non–planar structures. Very good linear relationships between the molecular dihedral angles and Hammett’s p–substituent constants were obtained. Electron–donating substituents increase the planarity of the substituted benzoyl group that involves phenyl ring A of the molecules, as well as the folding of phenyl ring B. The conformational equilibrium constants of o–hydroxy–benzophenones ranged approximately between 10–7–10–6. On the other hand, it was concluded that greater hydrogen–bond donor capability of a solvent increases the polarization of the compounds and consequently, increases their dipole moments. It was further concluded that the electron–donating groups increase the strength of the intramolecular hydrogen bond and that in the solvents used the o–hydroxy–benzophenones possess an important intramolecular hydrogen bond of the moderate classFil: Mantas, Athena. University of Toronto; CanadáFil: Blanco, Sonia Encarnacion. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Ferretti, Ferdinando Hector. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; ArgentinaBioChem Press2004-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/138375Mantas, Athena; Blanco, Sonia Encarnacion; Ferretti, Ferdinando Hector; The effects of substituents and solvents on the conformation of benzophenones; BioChem Press; Internet Electronic Journal of Molecular Design; 3; 7; 6-2004; 387-3991538-6414CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.biochempress.com/av03_0387.htmlinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:21:39Zoai:ri.conicet.gov.ar:11336/138375instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:21:39.334CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv The effects of substituents and solvents on the conformation of benzophenones
title The effects of substituents and solvents on the conformation of benzophenones
spellingShingle The effects of substituents and solvents on the conformation of benzophenones
Mantas, Athena
Substituted benzophenones
Effects of substituents and solvents
Conformational equilibrium
Hydrogen bonding
Ab initio and DFT methods
title_short The effects of substituents and solvents on the conformation of benzophenones
title_full The effects of substituents and solvents on the conformation of benzophenones
title_fullStr The effects of substituents and solvents on the conformation of benzophenones
title_full_unstemmed The effects of substituents and solvents on the conformation of benzophenones
title_sort The effects of substituents and solvents on the conformation of benzophenones
dc.creator.none.fl_str_mv Mantas, Athena
Blanco, Sonia Encarnacion
Ferretti, Ferdinando Hector
author Mantas, Athena
author_facet Mantas, Athena
Blanco, Sonia Encarnacion
Ferretti, Ferdinando Hector
author_role author
author2 Blanco, Sonia Encarnacion
Ferretti, Ferdinando Hector
author2_role author
author
dc.subject.none.fl_str_mv Substituted benzophenones
Effects of substituents and solvents
Conformational equilibrium
Hydrogen bonding
Ab initio and DFT methods
topic Substituted benzophenones
Effects of substituents and solvents
Conformational equilibrium
Hydrogen bonding
Ab initio and DFT methods
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Motivation. Natural and synthetic benzophenones are compounds of great scientific and applied interest due to the varied biological and physicochemical properties that they posses. As part of a program aimed at investigating new physicochemical properties of substituted benzophenones, we carry out a study on the influence of the substituents and solvents upon the molecular conformations of these compounds. In the future, we expect to propose relationships between the molecular structural parameters with diverse experimental properties of the compounds that are currently being determined in our laboratory. Method. The HF/6–31G(d) and B3LYP/6–31G(d) methods were used for calculations. Onsager’s and Tomasi’s models were used to analyze the solvent effects on the nine benzophenones studied. Results. A conformational equilibrium was proposed between the two conformers of benzophenones with the greatest thermodynamic stability. The total energies, torsional angles, dipole moments, structural and reactivity molecular parameters, and conformational equilibrium constants were calculated in vacuum, ethanol, methanol and water. The calculated magnitudes were correlated with Hammett’s substituent constants and parameters of solvating solvents. Conclusions. The benzophenones investigated have non–planar structures. Very good linear relationships between the molecular dihedral angles and Hammett’s p–substituent constants were obtained. Electron–donating substituents increase the planarity of the substituted benzoyl group that involves phenyl ring A of the molecules, as well as the folding of phenyl ring B. The conformational equilibrium constants of o–hydroxy–benzophenones ranged approximately between 10–7–10–6. On the other hand, it was concluded that greater hydrogen–bond donor capability of a solvent increases the polarization of the compounds and consequently, increases their dipole moments. It was further concluded that the electron–donating groups increase the strength of the intramolecular hydrogen bond and that in the solvents used the o–hydroxy–benzophenones possess an important intramolecular hydrogen bond of the moderate class
Fil: Mantas, Athena. University of Toronto; Canadá
Fil: Blanco, Sonia Encarnacion. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentina
Fil: Ferretti, Ferdinando Hector. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Química. Área de Química Física; Argentina
description Motivation. Natural and synthetic benzophenones are compounds of great scientific and applied interest due to the varied biological and physicochemical properties that they posses. As part of a program aimed at investigating new physicochemical properties of substituted benzophenones, we carry out a study on the influence of the substituents and solvents upon the molecular conformations of these compounds. In the future, we expect to propose relationships between the molecular structural parameters with diverse experimental properties of the compounds that are currently being determined in our laboratory. Method. The HF/6–31G(d) and B3LYP/6–31G(d) methods were used for calculations. Onsager’s and Tomasi’s models were used to analyze the solvent effects on the nine benzophenones studied. Results. A conformational equilibrium was proposed between the two conformers of benzophenones with the greatest thermodynamic stability. The total energies, torsional angles, dipole moments, structural and reactivity molecular parameters, and conformational equilibrium constants were calculated in vacuum, ethanol, methanol and water. The calculated magnitudes were correlated with Hammett’s substituent constants and parameters of solvating solvents. Conclusions. The benzophenones investigated have non–planar structures. Very good linear relationships between the molecular dihedral angles and Hammett’s p–substituent constants were obtained. Electron–donating substituents increase the planarity of the substituted benzoyl group that involves phenyl ring A of the molecules, as well as the folding of phenyl ring B. The conformational equilibrium constants of o–hydroxy–benzophenones ranged approximately between 10–7–10–6. On the other hand, it was concluded that greater hydrogen–bond donor capability of a solvent increases the polarization of the compounds and consequently, increases their dipole moments. It was further concluded that the electron–donating groups increase the strength of the intramolecular hydrogen bond and that in the solvents used the o–hydroxy–benzophenones possess an important intramolecular hydrogen bond of the moderate class
publishDate 2004
dc.date.none.fl_str_mv 2004-06
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/138375
Mantas, Athena; Blanco, Sonia Encarnacion; Ferretti, Ferdinando Hector; The effects of substituents and solvents on the conformation of benzophenones; BioChem Press; Internet Electronic Journal of Molecular Design; 3; 7; 6-2004; 387-399
1538-6414
CONICET Digital
CONICET
url http://hdl.handle.net/11336/138375
identifier_str_mv Mantas, Athena; Blanco, Sonia Encarnacion; Ferretti, Ferdinando Hector; The effects of substituents and solvents on the conformation of benzophenones; BioChem Press; Internet Electronic Journal of Molecular Design; 3; 7; 6-2004; 387-399
1538-6414
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.biochempress.com/av03_0387.html
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv BioChem Press
publisher.none.fl_str_mv BioChem Press
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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