O. Hammerich — Organic Electrochemistry (Fifth edition, 2016)

Автор: O. Hammerich
Название книги: Organic Electrochemistry (Fifth edition, 2016)
Формат: PDF
Жанр: Химия
Страницы: 1717
Качество: Изначально компьютерное, E-book

Highlights from the Fifth Edition:
Coverage of the electrochemistry of buckminsterfullerene and related compounds, electroenzymatic synthesis, conducting polymers, and electrochemical fluorination
Systematic examination of electrochemical transformations of organic compounds, organized according to the type of starting materials
In-depth discussions of carbonyl compounds, anodic oxidation of oxygen-containing compounds, electrosynthesis of bioactive materials, and electrolyte reductive coupling
Features 16 entirely new chapters, with contributions from several new authors who also contribute to extensive revisions throughout the rest of the chapters
Completely revised and updated, Organic Electrochemistry, Fifth Edition explains distinguishing fundamental characteristics that separate organic electrochemistry from classical organic chemistry. It includes descriptions of the most important variants of electron transfers and emphasizes the importance of electron transfers in initiating various electrochemical reactions. The sweeping changes and lengthy additions in the fifth edition testify to the field’s continued and rapid growth in research, practice, and application, and make it a valuable addition to your collection.

Organic electrochemistry is concerned with the reduction and oxidation of organic molecules at
electrodes. Although it is now more than 200 years ago that the so-called Volta pile was discovered,
it was not until 1830–1850 that investigations of organic electrochemical processes, pioneered
by Faraday and Kolbe, were established as a research area in their own right. Toward the end of
the nineteenth century, investigators such as Tafel and Haber made significant contributions to the
present knowledge of organic electrode processes. Haber, for instance, in his now famous paper
on the reduction of nitrobenzene (F. Haber, Z. Elektrochem. 1898, 4, 506) recognized the significance
of the electrode potential in the following words: “Oxydations- und Reduktionsprozesse hängen
in erster Linie von dem Potential der Elektrode ab, an welcher sie ablaufen, und Stromdichte,
Stromdauer und Elektrodenmaterial sind nur insofern bedeutsam, als sie das Elektrodenpotential
und seine Änderungen im Gang der Elektrolyse bestimmen.” (“Oxidation and reduction processes
primarily depend on the potential of the electrode at which they proceed, and current density, current
duration, and electrode material are only important insofar as they determine the electrode
potential and its changes during the electrolysis.”) The application of electrolysis as a means of
preparing organic compounds continued in the first half of the twentieth century. This development
took place along with the development of new electrochemical techniques for the study of electrode
processes, for instance, polarography at the dropping mercury electrode introduced by Heyrovsky
in the early 1920s. Other important contributions were due to Lingane, Kolthoff, Laitinen, and
Delahay. Later, Hickling’s potentiostat (A. Hickling, Trans. Faraday Soc. 1942, 38, 27) as an experimental
tool to control experiments led into the computerization era.
Most of the work reported before World War II was carried out in aqueous electrolyte solutions.
This situation changed after the war, and since the mid-1950s, the attention has been focused
mostly on the application of nonaqueous solvents. This has allowed for the detection of the primary
intermediates, typically radical anions and radical cations, and for the study of their reactions. The
theoretical foundations for the analysis of kinetics and mechanisms by, for instance, cyclic voltammetry
and related techniques were mostly published in the 1960s and 1970s. The application of such
techniques has resulted in a steadily increasing understanding of the kinetics and mechanisms of
organic electrochemical processes.
Facing the fact that thousands of organic electrochemical processes are now known, it is striking
that most often the only electrochemical reaction to be mentioned in a typical organic chemistry
textbook is the oxidation of an organic carboxylic acid R-COOH to the corresponding dimeric
alkane R-R reported by Kolbe as early as 1849. Also, it is often overlooked that reductions by metals
involving radical anions as intermediates are intimately related to cathodic reductions. And
most frequently, radical cations are not mentioned at all, except, of course, in the context of mass
spectrometry! This problem, that organic electrochemistry has had difficulties in penetrating into
the organic chemistry curriculum, was pointed out already in the preface to the first edition of this
book. Unfortunately, not much has changed in the more than 40 years that have elapsed between
that edition and this fifth edition.
The knowledge of organic electrochemistry had in the 1960s and the early 1970s matured to the
point where the time was ripe for the first edition of Organic Electrochemistry (M.M. Baizer, ed.,
Organic Electrochemistry, Marcel Dekker: New York, 1973). The editor was Manual M. Baizer,
well known for his contributions to preparative organic electrochemistry, first of all the development
of the electrohydrodimerization of acrylonitrile into a highly successful industrial process for
the manufacture of adiponitrile. Baizer set the standards for the book that was organized to include
chapters both on the electrochemical reduction and oxidation of specific classes of compounds and on specific types of electrode processes. This approach obviously led to some overlap, a problem that
Baizer touched upon in the following words: “It has become routine, at least for reviewers, to point
out that in a multi-authored book there is overlap of material, non-uniformity of style, repetition etc.
This book was not hastily assembled, and there was adequate time to achieve uniformity if that had
been desired. But the material was deliberately organized so that a given segment might appear in
two or more contexts and, further, where unanimity of opinion does not exist, more than one current
viewpoint might be expressed.” The same basic philosophy was followed in the organization of the
second (Baizer, M.M., Lund, H., eds., Organic Electrochemistry, Marcel Dekker: New York, 1983),
third (Lund, H., Baizer, M.M., eds., Organic Electrochemistry, Marcel Dekker: New York, 1991),
fourth (Lund, H., Hammerich, O., eds., Organic Electrochemistry, Marcel Dekker: New York, 2001)
editions, and now for this fifth edition. Owing to this intentional overlap between chapters, the reader
is encouraged to use the index to find details, in addition to those found in a given chapter, of the
electrochemistry of a specific compound or a class of compounds. Also, some formal variations that
reflect common usage by different authors have not been brought into line, for example, the use of “e”
or “e−” for the electron or the nomenclature of electrochemical mechanisms (“ECE” vs. “eCe,” etc.).
The progress in organic electrochemistry that has taken place since the appearance of the fourth
edition is reflected by the organization of this edition. Organic electrochemical reactions are rather
complex with electron transfers and transport processes interwoven with bond breaking and forming
reaction steps. As a consequence, different perspectives have developed over the years and organic
electrochemistry may be discussed following different lines of thought. Moreover, organic electrochemical
reactions are often integrated into more complicated synthetic strategies and advanced
chemical reasoning or are applied to complex materials and structures. Consequently, it was decided
to present the field as follows. After an introduction of some basic and technical aspects, the reaction
step that distinguishes organic electrochemistry from classical organic reactions, the electron
transfer to and from organic molecules, is described and its most important variants are presented.
Second, the importance of electron transfers for the initiation of various organic electrochemical
reaction types (follow-up reactions) is emphasized. Third, the electrochemical transformations of
organic compounds are systematically presented according to the type of starting materials. Finally,
cases where organic electrochemistry forms an integral part in a wider context of chemical research
(e.g., in biological or materials science) are discussed.
In comparison with the fourth edition, the following major changes have been made to this
edition:
Sixteen new chapters have been included. These are:
• Chapter 3: In Situ Spectroelectrochemistry of Organic Compounds by Peter Rapta, Evgenia
Dmitrieva, Alexey A. Popov, and Lothar Dunsch
• Chapter 4: Surface Techniques by Mohamed M. Chehimi, and Jean Pinson
• Chapter 5: The Application of Digital Simulation by Bernd Speiser
• Chapter 6: Theoretical Calculation of Reduction Potentials by Junming Ho, Michelle L.
Coote, Christopher J. Cramer, and Donald G. Truhlar
• Chapter 8: The Application of Ionic Liquids, Emulsions, Sonication, and Microwave
Assistance by John D. Watkins and Frank Marken
• Chapter 9: Combinatorial Electrochemistry and Miniaturization by Kevin D. Moeller
• Chapter 11: Influence of Molecular and Medium Effects on Two-Electron Processes by
Kevin Lam and William E. Geiger
• Chapter 12: Electrochemically Driven Supramolecular Devices by Paola Ceroni, Alberto
Credi, and Margherita Venturi
• Chapter 13 and 14: Proton-Coupled Electron Transfers and Dissociative Electron Transfers
by Cyrille Costentin, Marc Robert, and Jean-Michel Savéant
• Chapter 15: Electron Transfer Catalyzed Reactions by Kazuhiro Chiba and Yohei Okada
• Chapter 24: Activation of the Carbon-Halogen Bond by Armando Gennaro, Abdirisak
Ahmed Isse, and Patrizia Romana Mussini
• Chapter 36: Organometallic Compounds as Tools in Organic Electrosynthesis by Anny
Jutand
• Chapter 40: Electrochemical Modeling of Biological Processes by Richard D. Webster
• Chapter 42: Surface-Bound and Immobilized Molecules by Jean Pinson
• Chapter 44: Electrocatalytic Hydrogenation by Jean Lessard
Approximately one-fourth of the previous chapters have been rewritten by new authors:
• Chapter 7: Preparative Electrolysis on the Laboratory Scale by Jakob Jörissen and Bernd
Speiser
• Chapter 16: Cleavages and Deprotections by Ole Hammerich
• Chapter 26: Oxygen Containing Compounds: Alcohols, Ethers, and Phenols by Robert
Francke, Thomas Quell, Anton Wiebe, and Siegfried R. Waldvogel
• Chapter 27: Sulfur, Selenium, and Tellurium Containing Compounds by Richard S. Glass
• Chapter 30: Reduction of Nitro Compounds and Related Substrates by Ole Hammerich
• Chapter 31: Reduction of Aldehydes, Ketones, and Azomethines by Jiri Ludvik
• Chapter 32: Reduction of Carboxylic Acids and Derivatives by Rolf Breinbauer and Martin
Peters
• Chapter 34: Heterocyclic Compounds by Fructuoso Barba and Belen Batanero
• Chapter 39: Electroenzymatic Synthesis by Christina Kohlmann and Stephan Lütz
All other chapters have been thoroughly revised or updated where needed, in some cases in cooperation
with new coauthors.
The following four chapters have been omitted:
• Old Chapter 4: Comparison Between Electrochemical Reactions and Chemical Oxidations
and Reductions
• Old Chapter 28: Amalgam and Related Reductions
• Old Chapter 29: Electrogenerated Reagents
• Old Chapter 31: Industrial Electroorganic Chemistry
Thus, in a sense, this is a new book and not just a conservative update to the previous edition.
Altogether this book encompasses 44 chapters written by 66 authors.
In most cases, we have encouraged authors to avoid back references to the fourth edition.
However, this was not always possible, nor desirable. The text of some chapters in the fourth edition
is still authoritative and not much could be added (see, e.g., the appendices on solvents and supporting
electrolytes in Chapter 7).
Many of the authors of the fourth and previous editions have now retired. Fortunately, new
authors have willingly accepted to carry the torch on to this new edition. Sadly, one of these new
authors, Lothar Dunsch, passed away in late 2013. This was a great loss to the electrochemical community,
and he will be remembered as one of the leading figures in the development and application
of spectroelectrochemistry.