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Rating 3.7 Dimethyl fumarate is a Z-substituted ole n. It has a low-lying LUMO which is not polarized due to the symmetrical substitution. Because of the low-lying LUMO, dimethyl fumarate is susceptible to nucleophilic attack. On the other hand, vinyl acetate is an ole n with an X: substituent at one end. The HOMO is polarized away from the substituent acetoxy group, OAc. Since the HOMO is also raised in energy as a result of the interaction, vinyl acetate would be particularly susceptible to electrophilic attack, the preferred site being the C atom to the substituent. Addition of a radical to dimethyl fumarate generates a Z-substituted carbon free radical. Addition of a radical to vinyl acetate generates an X:-substituted carbon free radical. Each of the two possible types of radicals has an equal probability of encountering either ole n. The situation is depicted in Figure 7.4 The low-lying SOMO of the electrophilic fumarate radical (left) interacts preferentially with the high HOMO of vinyl acetate, leading to selective formation of the acetoxy radical (right). The high SOMO of the acetoxy radical interacts most strongly with the low LUMO of dimethyl fumarate with selective formation of the fumarate radical. And so on. Radical stabilities may be measured experimentally by the determination of homolytic bond dissociation energies (BDEs) in the gas phase [140] or in solution by relating them empirically to the pKHA and the oxidation potentials, Eox A of weak acids, online pdf editor for windows 10 free: Classic PDF Editor - Free download and software reviews - CNET ... pdf editor software for windows 7 free download Best Windows 10 Apps to View and Edit PDFs in 2019 | Windows ...
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