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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/138375
Ver los metadatos del registro completo
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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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1844614205773185024 |
score |
13.070432 |