scispace - formally typeset
Search or ask a question
Journal ArticleDOI

Aromatic Oxidation by Electron Transfer. I. Oxidations of p-Methoxytoluene

01 Dec 1966-Journal of the American Chemical Society (American Chemical Society)-Vol. 88, Iss: 23, pp 5473-5478
About: This article is published in Journal of the American Chemical Society.The article was published on 1966-12-01. It has received 118 citations till now. The article focuses on the topics: Electron transfer.
Citations
More filters
Book
Lennart Eberson1
01 Jan 1987
TL;DR: The electron transfer reaction between two species of different chemical composition has been studied extensively in the literature as discussed by the authors, where electron transfer reactions constitute the basis of theoretical treatments of electron transfer and self-exchange reactions.
Abstract: Publisher Summary This chapter focuses on the electron transfer reactions in organic chemistry. The simplest elementary act in homogeneous solution chemistry is the exchange of an electron between two chemical entities. No bonds need to be formed or broken in the process, and if the two species are identical, except for a difference in oxidation state, no net chemical change takes place. Such self-exchange reactions constitute the basis of theoretical treatments of electron transfer. A more complex and chemically interesting situation is the electron-transfer reaction between two species of different chemical composition. In electron-transfer theory, it is an important postulate that electrons are transferred one by one, which does not mix well with the two-electron centered electronic theory of organic molecules. Organic electron transfers rarely occur as isolated steps because of the high chemical reactivity of odd-electron species. Processes involving one or several electron-transfer steps are not likely to preserve the stereochemical integrity of the reactants. With the present upsurge of research studies frequently invoking organic electron-transfer steps in mechanistic discussions, there is a great need of a theoretical background applicable to organic species and compatible with the language of physical organic chemistry.

446 citations

Book ChapterDOI
TL;DR: In this article, the subject of metal-catalyzed oxidations of organic compounds in the liquid phase, largely within a mechanistic framework, has been discussed and a better understanding of the catalytic action of metal complexes is essential from the view of increasing selectivity and efficiency.
Abstract: Publisher Summary The liquid phase oxidation of hydrocarbons by molecular oxygen forms the basis for a wide variety of petrochemical processes including the manufacture of phenol and acetone from cumene, adipic acid from cyclohexane, terephthalic acid from p -xylene, acetaldehyde and vinyl acetate from ethylene, and propylene oxide from propylene. The majority of these processes employ catalysis by transition metal complexes to attain maximum selectivity and efficiency. This chapter describes the subject of metal-catalyzed oxidations of organic compounds in the liquid phase, largely within a mechanistic framework. A better understanding of the catalytic action of metal complexes is essential from the point of view of increasing selectivity and efficiency. Metal-catalyzed oxidations may be conveniently divided into two types—homolytic and heterolytic. The homolytic catalysis involves soluble transition metal salts (homogeneous), such as the acetates or naphthenates of Co, Mn, and Cu, or the metal oxides (heterogeneous). Heterolytic catalysis involves reactions of organic substrates coordinated to transition metals.

251 citations

Book ChapterDOI
TL;DR: A large number of electrochemical techniques are available for producing and studying cation radicals (or other electrogenerated) and their instrumentation, techniques, and theory are described in this paper.
Abstract: Publisher Summary This chapter discusses chemical oxidations, oxidations on acidic surfaces, and photoionizations. The formation of cation radicals in solution is also discussed. The chapter outlines the experimental techniques that have been used to study cation radicals and the type of information that can be obtained about their behavior. Examples of such investigations are provided. A large number of electrochemical techniques is available for producing and studying cation radicals (or other electrogenerated). Their instrumentation, techniques, and theory are described. The electrochemical techniques can be separated into two classes: the microelectrode or voltammetric techniques and the bulk electrolysis or coulometric techniques. Detailed descriptions of physical properties of cation radicals are presented in the chapter. Cation radicals react with a variety of nucleophiles. Substitution often occurs, but there are many examples in which electron transfer occurs either entirely or in part.

151 citations

Book ChapterDOI
TL;DR: In this article, two mechanisms are proposed for the dimerization of cation radicals of anisoles and related compounds, termed as radical-substrate coupling (RSC) and radical-surface coupling (RRD).
Abstract: Publisher Summary The dimerization of cation radicals of simple benzene derivatives is usually accompanied by the formation of the corresponding biphenyl derivative. This, by virtue of the extended conjugation is more easily oxidized, and frequently only intractable tars are found as final products. If the reaction medium is carefully selected, so that the biphenyl cation radicals are stable, useful synthetic procedures can be developed. Two mechanisms are probable for the dimerization of cation radicals of anisoles and related compounds. They are termed “radical–radical dimerization” (RRD) and “radical–substrate coupling” (RSC). The oxidation of aromatic hydrocarbons and alkylaromatic compounds in media of low nucleophilicity results in the formation of dimers. The cation radicals of triphenylamines form dimers in high yield when generated in acetonitrile. The products are tetraphenylbenzidines.

137 citations

Journal ArticleDOI
TL;DR: In this article, it is suggested that fluorination with high valency metal fluorides (e.g. AgF2, CoF3, MnF3 and CeF3) involves the initial oxidation of the substrate by the metal ion either to a radical-cation or, less commonly, by the abstraction of a hydrogen atom.

82 citations