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Doctoral Thesis
DOI
10.11606/T.46.2018.tde-28032018-140120
Document
Author
Full name
Emilí Bueno
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2003
Supervisor
Committee
Olivato, Paulo Roberto (President)
Emerenciano, Vicente de Paulo
Moran, Paulo José Samenho
Rittner Neto, Roberto
Temperini, Marcia Laudelina Arruda
Title in Portuguese
Estudo conformacional e das interações eletrônicas em: -fenilacetatos de etila para substituídos e suas formas mono- e di-oxigenadas e a-feniltioacetatos de etila e sua forma mono oxigenada
Keywords in Portuguese
Compostos de enxofre (Estudo)
Compostos de oxigênio (Estudo)
Espectroscopia infravermelha (Uso)
Físico-química orgânica
Interação química (Estudo)
Abstract in Portuguese
A presente tese relata o estudo conformacional e das interações eletrônicas de algumas α-feniltio-acetatos de etila para-substituídos e suas formas mono- e di-oxigenadas EtOC(O)CH2SOn-Φ-X (p) (I) e de alguns α-feniltio-tioacetatos de etila para-substituídos e sua forma mono-oxigenada EtSC(O)CH2SOn-Φ-X (p) (II), [ n =0 (a), 1 (b) e 2 (c) para (I)] e [n= 0 (a) e 1 (b) para (II)], sendo X substituintes atraentes, hidrogênio e doadores de elétrons. Este estudo foi realizado através da espectroscopia no infravermelho e cálculos ab initio HF/6-31G**. Nos α-ester-sulfetos (Ia) e α-tioester-sulfetos (IIa) as conformações gauche são fortemente estabilizadas pelas interações orbitalares π*co/ σc-s (hiperconjugativa) e π*co/ns. Nos β-ester-sulfóxidos (Ib) e β-tioester-sulfóxidos (IIb) enquanto a s conformações gauche são estabilizadas pela interação orbitalar πco/ σ*c-so, a conformação cis é estabilizada pela interação no(co)→π*SO. Nas β-ester-sulfonas (Ic) o confôrmero menos polar e mais estável gauche é fortemente estabilizado pelas interações Coulombicas e orbitalares Oδ-(CO) → Sδ+(SO2) e Oδ-(SO2) → Cδ+(CO), enquanto que o confôrmero gauche 1 é estabilizado por esta ultima interação e desestabilizado pela interação repulsiva entre os oxigênios negativamente carregados dos grupos C(O)OEt e SO2Et.
Title in English
Conformational and electronic interaction study in: ethyl α-phenylthio-acetates and their mono-and di-oxygenated derivatives and ethyl α-phenylthio-thioacetates and their mono-oxygenated derivatives
Keywords in English
Chemical interaction (Study)
Infrared spectroscopy (Use)
Organic physicochemistry
Oxygen compounds (Study)
Sulfur compounds (Study)
Abstract in English
This thesis reports the conformational and electronic interaction studies of some ethyl α-phenylthio-acetates and their mono-and di-oxygenated derivatives EtOC(O)CH2SOn-Φ-X (I) [for n=0 (a), l(b), and 2 (c)] and some ethyl α-phenylthio-thioacetates and their mono-oxygenated derivatives EtSC(O)CH2SOn-Φ-X (II) [for n= 0 (a) and 1 (b)], bearing at the para position electron-attracting, hydrogen and electron-donating substituents. This study was performed by means of infrared spectroscopy and HF/6-31G** ab initio calculations. For the β-ester-sulfides (Ia) and β-thioester-sulfides (IIa) the more stable gauche conformers are strongly stabilised by the π*co/ σc-s and π*co / ns orbital interactions. As for the β-ester-sulfoxides (Ib) and β-thioester-sulfoxides (IIb) while the gauche conformers are stabilised by the πco/ σ*c-s orbital interaction, the cis conformer is stabilised by the no(co) → π∗co interaction. For the β-ester-sulfones (Ic) the least polar and most stable gauche rotamer is strongly stabilised by the crossed Oδ-(CO)→ Sδ+(SO2) and Oδ-(SO2)→ Cδ+(CO) Coulombic and orbital interactions, while the least stable gauche1 rotamer is stabilised by this latter interaction and destabilised by the repulsive interaction between the negatively charged oxygen atoms of the C(O)OEt and SO2Et groups.
 
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Publishing Date
2018-04-23
 
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