Chapters authored
Reactivity of a Simplest Conjugated Diolefin in Liquid-Phase Oxidation: Mechanisms and Products
Ethylene is the simplest member of olefin series, but butadiene-1,3 (BD) is the simplest conjugated diolefin. In this chapter, we describe liquid-phase oxidations of BD with an emphasis on comparison of the diolefin with monoolefins. BD interacts with oxygen to form polyperoxide, whose thermal decomposition or hydrogenation leads to the formation of 2-butene-1,4-diol, 3-butene-1,2-diol, or butanediols together with furan and acrolein. BD can be oxidized in polar solvents by radical chain route to form directly the dioxygenates. Metal catalysts are able to control the oxidation by promoting formation of 2-butene-1,4-diol, 4-hydroxybut-2-enal, and furan. PdTe/C catalyst is applied in industry to produce 2-butene-1,4-diol diacetates with selectivity of 98%. The outstanding selectivity of the catalyst is caused by combined action of components in nonradical route and esterification of final product in acetic acid. Similar reaction in methyl alcohol yields 1,4-dimethoxy-2-butene, but with lower efficiency. The nonradical mechanism is firmly established for epoxidation of BD with hydrogen peroxide catalyzed by phosphotungstates. The selectivity of BD and hydrogen peroxide conversion to 3,4-epoxy-1-butene around 100% is attained. Analysis of published information and our own studies show many similarities in oxidation of BD and light olefins, which are very useful for understanding the mechanisms.
Part of the book: Alkenes