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Aromatic compounds homogeneous catalysis

Benzylic oxidation of aromatic side-chains is also a well established technology in the bulk chemicals arena, e. g. toluene to benzoic acid and p-xylene to ter-ephthalic acid [1,2]. These processes involve homogeneous catalysis by, e. g., cobalt compounds, however, and also fall outside the scope of this book. Ammoxi-dation of methyl-substituted aromatic and heteroaromatic compounds is performed over heterogeneous catalysts in the gas phase but this reaction is treated elsewhere (Section 9.5). Transition metal-substituted molecular sieves have been widely studied as heterogeneous catalysts for oxidation of aromatic side-chains in the liquid phase, but there are serious doubts about their heterogeneity [5,6]. Here again, a cursory examination of the literature reveals that supported palladium seems to be the only heterogeneous catalyst with synthetic utility [4]. [Pg.519]

Normally, a transition metal is the best catalyst to carry out the hydrogenation of aromatic compounds under both homogeneous and heterogeneous conditions that means in solution or in two-phase mode, respectively. Since the type of metal catalyst and its behavior strongly depend on the reaction conditions, both classes of catalysis will be considered separately in the following sections. [Pg.345]

Base catalysis is most effective with alkali metals dispersed on solid supports or in the homogeneous form as aldoxides, amides, and so on. Small amounts of promoters may be added to form organoalkali compounds that really have the catalytic power. Basic ion exchange resins also are useful. Some base-catalyzed processes are isomerization and oligomerization of olefins, reaction of olefins with aromatics, and hydrogenation of polynuclear aromatics. [Pg.563]

The indirect reduction of many organic substrates, in particular alkyl and aryl halides, by means of radical anions of aromatic and heteroaromatic compounds has been the subject of numerous papers over the last 25 years [98-121]. Many issues have been addressed, ranging from the exploration of synthetic aspects to quantitative descriptions of the kinetics involved. Saveant et al. coined the expression redox catalysis for an indirect reduction, in which the homogeneous reaction is a pure electron-transfer reaction with no chemical modification of the mediator (i.e., no ligand transfer, hydrogen abstraction, or hydride shift reactions). In the following we will consider such reactions and derive the relevant kinetic equations to show the kind of kinetic information that can be extracted. [Pg.571]

Dithianes and gemdithioacetals could be alternatively oxidized indirectly by means of the redox catalysis method. The technique appeared to be particularly mild and mainly avoided inhibition and adsorption phenomena relative to the anode platinum interface. Thus aromatic hydrocarbons (e.g. 9,10-diphenylanthracene) [83] and judiciously substituted triphenylamines [84] afford quite stable cation radicals used homogeneously as oxidants. Their standard potential, E°x, will determine the rate of electron exchange with the concerned sulfur compound. The cleavage of a C—S bond in any dithiane can be regarded as fast enough to draw the redox catalysis process to the indirect oxidation. [Pg.351]


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See also in sourсe #XX -- [ Pg.453 ]




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