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Book Review Adsorption of Molecules at Metal Electrodes. (Series Frontiers of Electrochemistry.) Edited by J. Lipkowski and P. N. Ross

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A little help is provided by the brief subject index; otherwise
the reader has to consult the original literature.
Nobody expects a book free of errors, and one can disregard misprints such as the resonance arrow for the Menschutkin reaction on page 1. More annoying is the use of
different letters to describe the same property, for example,
.d on pages 136-7, but a three pages later. On account of
the profusion of newly introduced symbols, this is very disturbing.
Whether the considerable time spent in understanding the
mathematics and terminology of this model pays off for the
“common” chemist, in order to describe experimental data
semi-quantitatively with a better theoretical basis, may be
left to his or her own discretion. The specialist familiar with
the authors’ original publications will probably not discover
much new material. Most of the diagrams in this book have
also been taken from the primary literature, sometimes in
severely reduced form which makes them difficult to decipher.
To conclude: this book was meant to serve many, but
turns out to be superficial in many aspects. Apart from the
discussion about the quantitative validity of the model, the
form of the book means that it will probably be useful to few
other than specialists.
J: Jens Woqf
Organisch-Chemisches Institut
der Universitat Heidelberg (FRG)
Synthetic Fluorine Chemistry. Edited by G. A . Olah, R. D.
Chambers and G. K. Surya Prakash. Wiley, New York,
1992. XVII, 402 pp., hardcover 5 75.00.-ISBN 0-47154370-5
The properties of fluorine, both as an element and in its
compounds, differ so markedly from those of the other halogens that fluorine chemistry has developed as a distinct subject with its own special methods. Now, 106 years after elemental fluorine was first obtained, this branch of chemistry
has become so extensive that to review it all is scarcely possible, even for an expert in the field. Accordingly, the aim of
this book is not to present a systematic survey; instead it
consists of 17 chapters in which leading scientists from universities and industry give comprehensive reviews of selected
areas of inorganic and, more especially, organic fluorine
chemistry. The book is based on papers presented at a symposium on Synthetic Fluorine Chemistry, which was organized by the Loker Hydrocarbon Research Institute of the
University of Southern California in February 1990.
In Chapter 1 Schrobilgen describes the preparation and
Lewis acid behavior of noble gas fluoride cations. Christe,
Wilson, and Schack (Ch. 2) describe methods for replacing
fluorine by oxygen in fluorides and oxyfluorides. Aubke,
Cader, and Mistry (Ch. 3) present a comprehensive review of
transition metal derivatives of strong protonic acids and superacids. Seppelt (Ch. 4)describes the preparation and properties of compounds containing carbon-sulfur multiple bonds
stabilized by fluorine. Lagow, Bierschenk, Juhlke, and Kawa
(Ch. 5) report on direct fluorination methods for the synthesis of perfluoropolyethers and on possible areas of application for these compounds. Adcock (Ch. 6) describes aerosol
direct fluorination, claimed to be a universal method for
perfluorinations. Rozen (Ch. 7) describes electrophilic fluorinations of organic compounds using fluorine or other fluorinating agents. Olah and Li (Ch. 8) demonstrate that oniumpolyhydrogenfluorides have a wide range of applications as
fluorinating agents. Burton (Ch.9) describes the use of
AnRru.. CIicm. 1111. Ed. Engl. 1993. 32, No. 7
organometallic compounds containing perfluoroalkyl groups
for the synthesis of organofluoro compounds. Prakash
(Ch. 10) reports on nucleophilic perfluoroalkylations using
perfluorotrialkylsilanes. Farnham (Ch. 11) describes the use
of organosilicon reagents in synthetic organofluorine chemistry. Shteingarts (Ch. 12) discusses electrophilic ips0 reactions of polyfluoroarenes from the standpoint of synthetic
applications. Takenaka and Lemal (Ch. 13) discuss the perfluorobenzeneoxide-perfluorooxepin system. Krespan and
Dixon (Ch. 14) describe the chemistry of perhalogenated
dioxans and dioxens. Welch, Yamakazi, and Gimi (Ch. 15)
report on the Claisen rearrangement of fluoroacetamide aceta1 as a method for asymmetric syntheses of compounds of
biological interest. Chambers (Ch. 16) describes the preparation of some unusual fluorinated alkenes and dienes by reactions involving fluoride ions. Lastly Baum (Ch. 17) describes
syntheses of fluorinated monomers for condensation polymerization.
The book covers quite a broad range of topics and gives
a very good overview of the present state of experimental
fluorine chemistry. It includes about a thousand references
which afford a convenient way into the relevant literature.
There is a nine-page subject index which greatly facilitates
using the book as a reference source. The fact that i t originates from a symposium is readily apparent from the widely
differing styles of the chapters, some giving detailed treatments of only a few compounds while others treat many in
a brief manner. However, this variety makes the book agreeable to read for someone who, like this reviewer, works
through it from start to finish-for example, the reader who
is just beginning work in fluorine chemistry.
Stephan Riidiger
Projektgruppe Fluorchemie
Berlin (FRG)
Adsorption of Molecules at Metal Electrodes. (Series: Frontiers of Electrochemistry.) Edited by J. Lipkowski and
P. N. Ross. VCH Publishers, New York/VCH Verlagsgesellschaft, Weinheim, 1992. XI, 414 pp., hardcover
DM 246.00, $ 145.00.--ISBN 0-89 573-786-8, 0-89 573789-2 (set)/3-527-28008-1, 3-527-28007-3 (set)
An electrochemical double layer is formed at almost every
type of phase boundary. The driving forces causing this are
differences in the chemical potentials of the charge carriers
that are common to both phases, even though they may be
present in very different concentrations. The resulting electrical potential difference cannot be measured directly. Adsorbed molecules have a secondary effect on the electrochemical double layer. Where dipolar molecules are involved
there is not only a chemical interaction with the surface but
also a strong electrostatic field effect.
The volume reviewed here contains eight articles dealing
with the adsorption of molecules at metal electrodes. However, the topics covered are much more specialized than the
title leads one to expect. Of the metals considered, mercury
and platinum are by far the predominant ones. Where the
use of surface enhanced Raman spectroscopy (SERS) is described, silver and gold also feature, since these metals are
specific for the technique. The two most important utility
metals, iron and aluminum, are discussed only very briefly in
the article by Plieth et al. The other phase is an electrolyte
solution which contains not only the organic molecules but
also ions such as HSO, or CN- that can be adsorbed. The
methods used to study adsorption include the classical tech-
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1 107
niques of ellipsometry and optical reflection spectroscopy,
and also more modern methods such as infrared reflection
absorption spectroscopy (IRRAS), SERS, and Raman second harmonic spectroscopy. It has thus become possible to
obtain detailed information about the structure of the
double layer, the nature of the adsorption, and the dynamics
of phase transformations in monolayers. For example, benzonitrile molecules can be adsorbed in four different configurations relative to the electron lone pair of the nitrile group:
planar, bent so that the triple bond of the nitrile group has
a strong interaction with the surface through the formation
of either two o r four bonds, or “perpendicular”. In the first
two articles, by Guidelle and by Buess-Herman, the emphasis is on theoretical considerations and the use of molecular
models, whereas the remaining chapters report detailed experimental results obtained by the various surface analytical
techniques.
For the specialist this volume is undoubtedly a useful
source of detailed information on the theory and methodology of such studies, and it covers the literature up to the end
of the 1980s. Electrochemists can learn much from these
impressive results. However, the practitioner who wishes to
know, for example, how an acrylonitrile molecule lies on the
surface of a cadmium cathode (as in the Monsanto process
for the electrosynthesis of adiponitrile), o r how typical corrosion inhibitors are adsorbed on iron, will find no information here. Also it is regrettable that none of the authors has
taken the trouble to write a summary and evaluation of the
methods, but that is usually the case. The book will find its
way into libraries, but the high price is likely to deter individual scientists from buying it.
Fritz Beck
Fachgebiet Elektrochemie
der Universitat-Gesamthochschule Duisburg (FRG)
Tandem Organic Reactions. By Tse-Lok Ho. Wiley,
Chichester, 1992. X, 502 pp., hardcover $ 79.9.5-1SBN
0-471-57022-2
Tandem reactions, also called cascade, domino, sequential, o r one-pot reactions, are strictly speaking old hat. Perhaps one of the best-known tactical combinations is the
Robinson tropinone synthesis, discovered more than 75
years ago, which makes four new 0 bonds from three components in biomimetic fashion, and also the Robinson annulation, which has proved so valuable in steroid synthesis.
Tse-Lok Ho, previously with the NutraSweet company in
Chicago and now at the National Taiwan University, a wellknown author and prolific writer, whose earlier books include Hard and Soft Acids in Organic Chemistry (Academic
Press, 1977), Carbon-Carbon Bond Formation in Terpene
Synthesis (VCH, 1988) and Polarity Control ,for Synthesis
(Wiley, 1991), has now produced a timely monograph on
tandem reactions, selecting examples right up to 1992.
After a short preface and an introduction (Chapter I),
tandem reactions are classified, as far as this is possible and
practical, by the last step of the sequence. The following 14
chapters deal with a wealth of practical examples, which
have been put together by the author thanks to his wide
knowledge of the literature and excellent memory, and also
from his previous books. All methods for making carboncarbon bonds are represented, including ionic, pericyclic,
free radical, and transition metal mediated transformations.
The headings of the 14 chapters are as follows: 2. Aldol
Condensation; 3. Michael Reactions; 4. Tandem Vicinal Di1108
0 VCH Verlugsgesellschuf~mhH. 0-69451
Weinheim, 1993
functionalization of Alkenes and Alkynes; 5. Dieckmann
and Claisen Cyclizations; 6. Mannich Reactions; 7. DielsAlder Reactions; 8. Other Cycloadditions; 9. Retro-DielsAlder and Cheletropic Reactions; 10. Electrocyclic Reactions; 11. Ene, Retro-Ene, and Some Other Thermal
Reactions; 12. Sigmatropic Reactions; 13. Rearrangements
and Fragmentations; 14. Free Radical Reactions; 15. Miscellaneous Tandem Reactions.
However, the headings can only be a rough guide and
cannot give the full flavor of the diverse chemistry that is
described. For example, Chapter 4 contains examples of the
Pauson-Khand and the Dotz reaction as well as biosynthetically patterned cationic polyene cyclizations. Chapter 8 includes the Vollhardt [2 + 2 + 21 and also higher cycloadditions. Structurally simpler examples and also complex
natural products chemistry are well represented.
The structural formulas are well produced and capture the
essence of a procedure, with a concise commentary. Thus the
book complements and contrasts with other recent texts
which focus mainly on the tools of the trade, i.e. methods for
manipulating functional groups and the growing number of
reagents for organic synthesis. As far as I could see the book
contains no more than a few minor misprints and some inevitable misspellings of authors’ names.
Whither tandem reactions? As a strategem or even as a
principle of organic chemistry and synthesis, tandem reactions will undoubtedly continue to flourish. Elegance, aesthetic appeal, atom economy and functional group economy, convergence and also stereocontrol often blend to
provide optimum access to complex molecular structures. In
future it will be important to somehow measure the quality
of a tandem reaction, since the number of steps is not necessarily an absolute criterion, for example if the flexibility and
applicability are too narrow, or when it becomes too difficult
to find the “reaction window” which may not be wide
enough.“] In this case, it may still be possible that two or
three “inelegant” but well worked out steps are superior to
the elegant but difficult tandem procedure.”] Of course, the
time factor, so important for industry for obtaining material
for initial biological tests, may also be in favor of the linear
and more conventional step-by-step approach.
In summary, Tse-Lok Ho’s text is a welcome source book,
also for graduate seminars, and it is a must for a young
organic chemist setting out on his or her career. By exposing
gaps in our current knowledge the book, together with other
recent articles,L3- will stimulate discussion and new experimental work. Thus, it will help to evaluate the current state
of the art and synthetic efficiency.[”
H. Martin R. Hoffmann
Department of Organic Chemistry
University of Hannover (FRG)
For example, the important modification of using acetonedicarboxylic mid
instead of acetonedicarboxylic esfer in the tropinone synthesis was introduced by Schopf almost 20 years after Robinson’s first paper. See obituary
of Clemens Schopf by J. Thesing, Chem. Ber. 1979, 112, I-XIX.
The converse also applies. For example, the tandem bicyclization of P-keto
ally1 alcohols to 6.X-dioxahicyclo[3.2.l]octanes involves an unfavorable
hetero-Diels-Alder reaction in the first step, which is potentially reversible.
R
R
R
R
k
R
However, thanks to the hydroxy groups, the reaction is driven by the meversihle final cyclization (see Scheme). See also N. Daude, U. Eggert,
H. M. R. Hoffmann, J. Chem. Soc. Chem. Commun. 1988, 206; H. M. R.
oS70-~~833~93~o707-l/OR
$ 10.0Oi.2S/O
Avgew. Chem. Inl. Ed. EngI. 1993, 32, No. 7
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