Search results for "Methyl vinyl ether"
showing 6 items of 6 documents
ChemInform Abstract: Influence of Reactant Polarity on the Course of the Inverse-Electron-Demand Diels-Alder Reaction. A DFT Study of Regio- and Ster…
2010
The molecular mechanisms for the inverse-electron-demand Diels−Alder reactions between nitroethene and three substituted ethenes (propene, methyl vinyl ether, and dimethylvinylamine) to give the corresponding nitroso cycloadducts have been characterized with density functional theory methods using the B3LYP/6-31G* calculational level. On the basis of stability arguments and molecular orbital analysis relative rates, regioselectivity, and stereoselectivity, the presence of Lewis acid catalyst modeled by the BH3 system and the inclusion of solvent effects as a function of the nature of substituent in the dienophile fragment are analyzed and discussed. The ortho attack mode presents transition…
Influence of Reactant Polarity on the Course of the Inverse-Electron-Demand Diels−Alder Reaction. A DFT Study of Regio- and Stereoselectivity, Presen…
1999
The molecular mechanisms for the inverse-electron-demand Diels−Alder reactions between nitroethene and three substituted ethenes (propene, methyl vinyl ether, and dimethylvinylamine) to give the corresponding nitroso cycloadducts have been characterized with density functional theory methods using the B3LYP/6-31G* calculational level. On the basis of stability arguments and molecular orbital analysis relative rates, regioselectivity, and stereoselectivity, the presence of Lewis acid catalyst modeled by the BH3 system and the inclusion of solvent effects as a function of the nature of substituent in the dienophile fragment are analyzed and discussed. The ortho attack mode presents transition…
A mechanistic study of the participation of azomethine ylides and carbonyl ylides in [3+2] cycloaddition reactions
2015
The participation of azomethine ylides (AYs) and carbonyl ylides (CYs) in [3+2] cycloaddition (32CA) reactions has been analysed at the DFT B3LYP/6-31G(d) level. The asymmetric substitution breaks the pseudodiradical character of the simplest three-atom-components (TACs), modifying their electrophilic and nucleophilic behaviours. These TACs react quickly towards electrophilic nitroethylene. However, while the reaction with AY takes place via a zw-type mechanism, the reaction with CY appears to take place via a pr-type mechanism. A different behaviour is found in the reactivity towards the nucleophilic methyl vinyl ether. While AY presents a high activation energy, CY presents a high reactiv…
1992
Semi-IPN's of different composition, based on linear poly(methyl vinyl ether) (PVME) and crosslinked polystyrene are studied using stress and birefringence measurements in simple elongation. From quasistatic stress-strain experiments at constant T(experiment)-Tg, it can be deduced that the stress results only from the deformation of the polystyrene network, while the PVME chains do not contribute to the macroscopic stress. The concentration dependence of the network modulus is adequately described by the rubber elastic theories
Continuous polymer fractionation of poly(methyl vinyl ether) and a new Kuhn-Mark-Houwink relation
1995
Continuous polymer fractionation (CPF) — a new large-scale method — was applied to the technical poly(methyl vinyl ether) (PVME) using toluence as solvent and petroleum ether as non-solvent. Two different devices served as fractionation apparatus, namely a column packed with glass beads and a set of mixer-settler extractors. Advantages and draw-backs of these devices are discussed. The experiments yielded numerous PVME fractions, varying in molar mass from 22 to 87 kg/mol and in molecular non-uniformity U = (M¯w/Mn) – 1 from 0,25 to 0,41 according to gel-permeation chromatography as compared with ca. U = 1,30 for the starting material. The following Kuhn-Mark-Houwink relation was establishe…