| Summary: | Made available in DSpace on 2015-05-14T13:21:23Z (GMT). No. of bitstreams: 1
arquivototal.pdf: 2208268 bytes, checksum: a713e84bf72b1325038dab0816e190d4 (MD5)
Previous issue date: 2009-11-27 === Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES === In this work the origin of the π−π-staking conformation stability of 5S
in the 8-acrylate phenylmenthol 5 was revisiting. The geometries of
5S and 5T conformers were optimized from HF method and the
MPW1B95 functional; and the geometries of the 11S and 11T
conformers have been optimized from HF, MP2 methods and
MPW1B95 functional. All calculations were performed on 6-311 + + G
(2d, 2p) 6d as level of calculation. Using the optimized geometries of
5S, 5T, 11S and 11T (from MPW1B95/6-311 + + G (2d, 2p) 6d),
were performed 15 energy single-point calculations, investigating
various computational methods (ab initio, DFT and semiempirical).
We also described the spectroscopic (1H NMR) and theoretical (DFT
and ab initio) studies of 3-naphytylpropylcrotonate (12) and 3-
naphytylpropylsorbate (21). The geometries of 12S and 12T
conformers have been optimized from MP2, HF methods and B3LYP,
LSDA and MPW1B95 functionals using 6-311+G(d,p) as calculation
level. Finally, we describe the synthesis of 12 and 21 (the
unpublished) in 3 steps of each synthesis (19% and 22% respectively
of total yields) and the trans geometries of 12T and 21T were
characterized as the most stable in the conformational equilibrium of
12 and 21. === Neste trabalho a origem do motivo para a maior estabilidade da
conformação de 5S no acrilato de 8-fenilmentol 5 foi investigada. As
geometrias dos confôrmeros 5S e 5T foram otimizadas nos métodos
HF e no funcional MPW1B95; e as geometrias dos confôrmeros 11S e
11T foram otimizadas nos métodos HF, MP2 e o funcional MPW1B95.
Todos os cálculos usaram 6-311++G(2d,2p)6d como nível de cálculo.
Usando as geometrias otimizadas de 5S, 5T, 11S e 11T (por
MPW1B95/6-311++G(2d,2p)6d), foram efetuados 15 cálculos de
energia no ponto, investigando metodologias computacionais variadas
(ab initio, DFT e semiempirico). Descrevemos também o estudo
espectroscópico (RMN 1H) e teórico (DFT e ab initio) do crotonato de
3-naftilpropila (12) e o sorbato de 3-naftilpropila (21). As geometrias
dos confôrmeros de 12S e 12T foram otimizadas com os métodos
MP2, HF e os Funcionais B3LYP, LSDA e MPW1B95 usando 6-
311+G(d,p) como nível de cálculo. Finalmente, descrevemos a
síntese total de 12 e 21 (inéditas na literatura) em 3 etapas de
síntese cada (19% e 22% respectivamente de rendimentos globais) e
caracterizamos por 1H RMN a geometria trans 12T e 21T como a
mais estável no equilíbrio conformacional de 12 e 21.
|
|---|
