Conformational preferences for some 3-(4′-substituted phenylsulfonyl)-1-methyl-2-piperidones through spectroscopic and theoretical studies

Olivato, Paulo R.; Santos, Jean M. M.; Cerqueira, Carlos R.; Vinhato, Elisângela; Zukerman-Schpector, Júlio; Ng, Seik Weng; Tiekink, Edward R. T.; Colle, Maurizio Dal

doi:10.1016/j.molstruc.2012.06.019

Cited by 6 publications

(8 citation statements)

References 22 publications

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“…The c 3 conformer is the least polar and least stable conformer. The summing up of the selected natural bond orbital delocalization orbital energies is practically the same (ca.136 kcal mol −1 ) for the c 1 , c 2 …”

Section: (Received 1 November 2012; Final Version Received 27 Januarymentioning

confidence: 91%

“…As part of our on-going research on the conformational and electronic interaction studies in β-thio-carbonyl compounds (1,2) utilizing IR spectroscopic and theoretical methods, the *Corresponding author. Email: prolivat@iq.usp.br 3-(4 -substituted phenylsulfanyl)]-1-methyl-2-piperidinones (3), which are the precursors of the title compounds, were synthesized and studied.…”

Section: Introductionmentioning

confidence: 99%

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Conformational preferences for some 3,3-bis[(4′-substituted phenylsulfanyl)]1-methyl-2-piperidinones through spectroscopic and theoretical studies

Olivato

Cerqueira

Contieri

et al. 2013

Journal of Sulfur Chemistry

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2013) Conformational preferences for some 3,3-bis[(4′-substituted phenylsulfanyl)]1-methyl-2-piperidinones through spectroscopic and theoretical studies, Journal of Sulfur Chemistry, 34:6, 617-626,The analysis of the IR carbonyl band of some 3,3-bis[(4 -substituted phenylsulfanyl)]1-methyl-2-piperidinones 1-5 bearing as substituents OMe 1, Me 2, H 3, Cl 4 and Br 5, supported by B3LYP/6-31G(d,p) calculations for 3, indicated the existence of three conformers in the gas phase and practically a single conformer in solution. In the gas phase, the c 1 conformer is less polar and slightly more stable than the most polar c 2 conformer. The c 3 conformer is the least polar and least stable conformer. The summing up of the selected natural bond orbital delocalization orbital energies is practically the same (ca.136 kcal mol −1 ) for the c 1 , c 2 and c 3 conformers of 3. Therefore, the trend of the [O δ− (CO) · · · H δ+ o−Ph ] (hydrogen bond) attractive electrostatic interactions along with the trend of the [O δ− (CO) · · · S δ− ] repulsive electrostatic interactions are the main factors which determine the observed computed relative populations for the c 1 (44%), c 2 (31%) and c 3 (25%) conformers. Moreover, the IR single carbonyl stretching band found (for 1-5) in solvents of increasing relative permissivity (CCl 4 , CHCl 3 , CH 2 Cl 2 , CH 3 CN), in agreement with polarisable continuum model calculations (for 3), show that the most polar c 2 conformer is practically unique in the solution (for 1-5), and the geometry is very close to that of the c 2 conformer in the solid state (for 1-4). = H = C = N = O = S Y = OMe 1, Me 2, H 3, Cl 4, Br 5 Most polar conformer (c 2 ) Y Y

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Section: (Received 1 November 2012; Final Version Received 27 Januarymentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Conformational preferences for some 3,3-bis[(4′-substituted phenylsulfanyl)]1-methyl-2-piperidinones through spectroscopic and theoretical studies

Olivato

Cerqueira

Contieri

et al. 2013

Journal of Sulfur Chemistry

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“…11,12,[53][54][55][56] The significance of the chemical or physical interactions between MET and radical species can be assessed by using the total sum of the delocalization energies, ΣE (2), obtained by summing the electron delocalization energies of all the significant interactions between the NBO orbitals of interacting molecules. 57,58 The ΣE (2) values are reported in Table 3. A larger ΣE (2) means that the interactions, resulting from electron delocalization from donor to acceptor NBO between MET and radicals, are more important.…”

Section: Natural Bond Order (Nbo) Analysismentioning

confidence: 99%

Influence of electron acceptors on the kinetics of metoprolol photocatalytic degradation in TiO₂ suspension. A combined experimental and theoretical study

et al. 2015

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ARTICLE This journal isMetoprolol (MET) belongs to a group of frequently used β 1 -blockers, which often occur in waste waters. The objective of this work was to employ liquid chromatography (LC) and total organic carbon methods to study the photocatalytic degradation of MET in UV irradiated aqueous suspensions of TiO 2 (Wackherr's "Oxyde de titane standard" and Degussa P25), in the presence of different electron acceptors such as molecular oxygen, hydrogen peroxide, potassium bromate, and ammonium persulfate. The degradation rates were found to be strongly influenced by the kind of electron acceptor and the type of catalyst. The optimal amount of hydrogen peroxide and potassium bromate was investigated as well. MET photocatalytic degradation was fastest in the presence of O 2 and potassium bromate with TiO 2 Degussa P25, while mineralization was most efficient in the presence of molecular oxygen alone. In all investigated cases, degradation followed a pseudo-first order kinetics. Reaction intermediates of MET degradation in the presence of different electron acceptors with both catalysts were studied in detail and a number of them were indentified using LC-ESI-MS/MS. The interactions with MET of reactive radical species relevant to this study ( − • 2 O , • OH, • 2 BrO , and − • 4 SO ) were theoretically investigated by means of density functional theory (DFT) computations. § Electronic supplementary information (ESI) available: Influence of electron acceptors on the kinetics of metoprolol photocatalytic degradation in TiO2 suspension. A combined experimental and theoretical study.− 2 8 2 O S , and − 3BrO , can act as electron acceptors to enhance the photodegradation efficiency. These electron acceptors can have several effects including: (I) avoidance of e − −h + recombination because of scavenging of conduction-band electrons; (II) increase of the concentration of • OH and (III) production of other oxidizing species that can enhance the oxidation rate of the substrate and of its intermediate compounds. 10

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“…(CO) ) desempenham um papel fundamental no equilíbrio conformacional de compostos carbonílicos α-sulfonil substituídos 50,61,62…”

Section: Interações Orbitalares E Eletrônicasunclassified

“…Por esta razão, optou-se por levar em consideração apenas as interações envolvendo o grupo carbonila e os substituintes etiltio e fenilselenila. As energias de estabilização resultante das interações orbitalares a , obtidas por NBO, para cada um dos confôrmeros dos três derivados da série constam na 2-(fenilsulfonil)-delta-valerolactamas50 , é possível devido à alta ocupância do orbital π* CO por causa da conjugação com o anel aromático (evidenciada pela elevada energia de interação π CC →π* CO , Tabela 5). A interação π* CO →σ* CSe é ca.…”

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Análise conformacional e estudo das interações eletrônicas de algumas (α-fenilseleno-α-etiltio)-,(α-fenilseleno-α-etilsulfinil)- e (α-fenilseleno-α-etilsulfonil)-acetofenonas-para-substituídas

Junior¹,

Rogério²

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Cer q ueir a J únio r , Carlo s Ro gério C4 1 6 a An á l i s e c o n f o r m acio nal e estud o d a s i nte r a ç õ e s e l e t r ô n i c a s de algumas (α-fenilseleno-α-etiltio)-(α-fenilseleno-α-etilsulfinil)-e (α-fenilseleno-α-etilsulfo nil)-aceto feno nas-para-sub s t i t u íd as / Car lo s Ro gér io Cerq ueira J únio r .-São P aulo , 201 2. 206p. T ese (d o u t o r a d o)-Instituto d e Química d a Universid ad e d e São P aulo. Dep ar tamento d e Química Fund amental. Or ientad o r : Olivato , P aulo Ro b erto 1. I so mer ia co nfo rmacio nal : Química orgânica 2. Interação eletrônica : Química orgânica I. T. III. Olivato , P aulo Ro b erto , o r ientad o r. 547 .036 CDD AGRADECIMENTOS Ao meu pai, minha mãe e minha irmã por tudo aquilo que eu certamente falharia em elencar. Ao Prof. Dr. Paulo Roberto Olivato pela orientação ao longo de todos esses anos. Ao Prof. Dr. Julio Zukermann-Schpector e seus colaboradores pelas estruturas de difração de raio-X e pela valiosa contribuição na análise e discussão dos dados cristalográficos. Aos amigos Professores Drs. Alessandro Rodrigues e Elisângela Vinhato pela amizade, paciência e contribuição inestimável ao meu aprendizado desde os tempos de Iniciação Científica. Aos amigos do Colóquio: Arnaldo, André, Thiago, Renato-Maurício, Bruno, Marina e Júlio pelo companheirismo de todo momento durante toda a difícil jornada da pós-graduação. Aos colegas de laboratório: Daniel, Jean, Bruna, Jéssica, Adriana, Roberto, Nelson e por todos os outros que passaram por nosso grupo de pesquisa ao longo desses anos. Aos funcionários da Central Analítica do IQ-USP pela presteza na realização dos experimentos de RMN, massas e análise elementar. Ao CNPq pela bolsa concedida. À FAPESP pelos auxílios de pesquisa, fundamentais para a manutenção e modernização da infraestrutura do nosso laboratório. Pesquisa desenvolvida com o auxílio do LCCA

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Conformational preferences for some 3-(4′-substituted phenylsulfonyl)-1-methyl-2-piperidones through spectroscopic and theoretical studies

Cited by 6 publications

References 22 publications

Conformational preferences for some 3,3-bis[(4′-substituted phenylsulfanyl)]1-methyl-2-piperidinones through spectroscopic and theoretical studies

Conformational preferences for some 3,3-bis[(4′-substituted phenylsulfanyl)]1-methyl-2-piperidinones through spectroscopic and theoretical studies

Influence of electron acceptors on the kinetics of metoprolol photocatalytic degradation in TiO₂ suspension. A combined experimental and theoretical study

Análise conformacional e estudo das interações eletrônicas de algumas (α-fenilseleno-α-etiltio)-,(α-fenilseleno-α-etilsulfinil)- e (α-fenilseleno-α-etilsulfonil)-acetofenonas-para-substituídas

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