вход по аккаунту


Book Review Stereochemistry of Radical Reactions. By D. P. Curran N. A. Porter and B

код для вставкиСкачать
price, covers all the essential aspects of the
study of chemical reactions as they progress towards an equilibrium state. The
author’s aim is is to teach the fundamental
concepts rather than to treat the subject in
minute detail. This has resulted in a book
that will be useful not only for physical
chemists but also for organic and inorganic chemists, whose work nowadays includes an increasing amount of kinetic
studies. Logan’s book covers reactions in
the gas phase, in solutions, and at solid
catalyst surfaces. Solid state kinetics has
rightly been excluded, as it is outside the
scope of a book of this kind. Each of the
twelve chapters, except for the last one,
ends with a set of exercise problems that
are intended to give deeper insights into
what has been learned. The data for the
examples are mostly taken from the chemical literature, thereby linking the discussion to real situations.
In Chapter 1 the author explains the
empirical framework of chemical kinetics.
After introducing the concept of the reaction rate he formulates a general rate
equation and uses this to explain the idea
of the order of a reaction. The rate equations for different reaction orders are integrated, and methods for determining the
reaction order are described. Lastly, the
temperature dependence of rate constants
is discussed on the basis of the Arrhenius
equation. Regrettably, this chapter contains several annoying errors. Thus, a minus sign is missing from Equation (1 .I l ) ,
the definition of the reaction rate. The
treatment of signs is again rather haphazard in the integration of the rate equation
for a first-order reaction [Equations (1.14)
and (1.15)]. In the integration of the rate
equation for a second-order reaction
(first-order in each of the two educts) the
author merely refers the student to “simple algebra” instead of explicitly setting
out the breakdown into partial fractions.
Here he fails to completely live up to his
assurance on the back cover of the book,
which states that the mathematics involved will be carefully explained for students with limited capabilities in that direction. The omission of units in the calculation of the activation energy from the
gradient of an Arrhenius plot (p. 19) is also
questionable from a teaching standpoint.
Chapter 2 is concerned with practical
aspects of planning and carrying out kinetic experiments. After discussing certain
minimal requirements (such as temperature control. rapid mixing of the reactants, and a clearly defined reaction path)
the author describes different methods for
monitoring the progress of reactions in
solutions : the “clock method”, polarimetry, spectrophotometry, electrical conduc-
(0VCH Vrrlup.s~esellschafimhH.
tivity measurements, and dilatometry.
For gas phase reactions the conventional
method of measuring the total pressure is
described, and also the possibility of using
mass spectrometry is discussed. A description of modern stopped-flow techniques is
followed by warnings about the risks of
errors being introduced when determining
rate constants, arising for example from
incorrect weighting in a linear regression
Chapter 3 deals with a number of simple
types of reaction mechanisms, such as sequential reactions, the formation of intermediate complexes, parallel reactions,
and opposing reactions, and discusses the
kinetic behavior resulting from these. The
important distinction between the molecularity and the order of a reaction is clearly explained. The author also introduces
the stationarity principle that is often used
in analyzing the subsequent stages. Chapter 4 discusses theoretical treatments of
bimolecular reactions (collision theory,
transition state theory, the theory of diffusion-controlled reactions in solutions).
Chapter 5 is concerned with the interpretation of measurements on bimolecuIar reactions in solutions, including the
Marcus theory for electron transfer reactions. After treating unimolecular gas
phase reactions in Chapter 6, the author
devotes Chapter I to chain reactions.
Chapters 9 and 10 then deal with the important subject of catalysis, including
such interesting aspects as oscillatory reactions and enzyme kinetics. The last
three chapters are devoted respectively to
studies of fast reactions using modern relaxation techniques, the reaction kinetics
of photochemically excited molecules,
and studies of elementary reactions in
crossed molecular beams.
The book is completed by two short appendices, brief answers to the exercise
problems, a keyword index, and an index
of reactions mentioned in the text. Despite
the minor shortcomings in Chapter 1 as
already mentioned, this is a valuable book
in which the author has succeeded in conveying an impression of a very broad
range of aspects of chemical kinetics in the
gas and solution phases and on solid catalysts. It provides the reader with a comprehensive overview encompassing both
the history of chemical kinetics and the
latest developments in the field.
In view of the reasonable price, Fundamentals of Chemical Kinetics can be recommended unreservedly for readers
seeking a broad introductory insight into
the subject.
Dirk Wilmer
Institut fur Physikalische Chemie
der Universitat Munster (Germany)
0-69451 Weinheim.1996
Stereochemistry of Radical Reactions.
By D.P. Curran, N . A . Porter and
B. Giese. VCH Verlagsgesellschaft,
Weinheim, 1995. 280 pp., hardcover
DM 148.00.-ISBN 3-527-29372-8
Until a decade ago, a researcher contemplating how to construct a carboncarbon bond stereoselectively would not
have considered radical reactions as a
method of choice. This is partly because
radical reactions with high stereoselectivity were an anomaly rather than the norm.
In the past ten years, however, one can
scarcely open a new issue of a journal
without seeing some work on stereoselective radical reactions. It is timely that
three leading experts in organic free radical chemistry, Professors Curran, Porter.
and Giese. have now written an outstanding monograph on stereoselective radical
The monograph is divided into six
chapters. In Chapter 1 the reader is introduced to the basic concepts required for
successful execution of a radical reaction
and to the general principles of stereoselectivity in ionic as well as radical reactions. A brief discussion of the different
methods for generating radicals is followed by a liberal citation of key reviews
and leading articles at the end of the chapter. The next four chapters discuss different aspects of stereoselective radical reactions. The reactions are classified according to substrate or chiral auxiliary
control of stereoselectivity. Chapter 2, a
major portion of the monograph, focuses
on stereocontrol in radical cyclizations.
The reactions in this chapter are further
classified on the basis of ring size. Although this is not intended to be an exhaustive treatment, the important factors
responsible for stereoselectivity in cyclizations are described in a very authoritative
and concise manner. A short section on
stereoselectivity of cyclizations under
group transfer conditions is also included.
The third chapter deals with aspects of
substrate controlled diastereoselectivity in
cyclic systems. The focus of this chapter is
again on control of stereochemistry in
radical reactions of five- and six-membered rings, systems which are generally
more selective. Chapter 4 discusses issues
of stereocontrol in radical reactions of
acyclic systems. The models used for explaining stereoselectivity in acyclic systems undergoing ionic reactions are extended to radical processes and are nicely
illustrated. Chapter 5 takes the reader
through chiral auxiliary mediated
diastereoselective reactions. This portion
of the monograph, reflecting the strengths
of the three authors, is well written and
0570-0833j96~3521-2542$ 15.00 ,2510
Angebv. Chrm. Int. Ed. Engl. 1996. 35, N o . 21
gives a detailed account of the present
state of knowledge of diastereoselective
radical reactions. The monograph ends
with a short chapter on stereoselectivity
occurring during radical combinations,
radical rearrangements, and formation of
alkenes from radical intermediates. The
information in this monograph gives
guidelines which should ensure that a scientist embarking on a stereoselective radical reaction has enough control over its
design and will be able to predict its outcome with reasonable confidence.
Overall. this is a very well written, easy
to read, and timely work on the stereochemistry of radical reactions. It is well
referenced and the citations are current up
to the beginning of 1995. The index at the
end is more than adequate. This is a “must
buy” book for libraries and practitioners
of organic free radical chemistry, o r for
scientists who wish to venture into the fascinating field of stereoselective organic
free radical reactions. The monograph
will be an excellent “recommended text”
for a graduate course on stereochemistry
or free radical chemistry.
Mukund P. Sibi
North Dakota State University
Fargo, N D (USA)
Free Radicals in Organic Chemistry.
By J. Fossy, D. Lgfort and J. Sorba.
Wiley, New York, 1995. 307 pp., paperback
$ 39.80.-ISBN
Development of new synthetic organic
methodology using free radical intermediates continues to advance at a rapid rate.
A n w c . Chcm. 1111 0 1 . EiigI. 1996, 3S, No. 2f
Although there are excellent monographs
and review articles on organic free radical
chemistry, there are no good textbooks.
With such an active and important branch
of organic chemistry, if one is required to
teach an upper level undergraduate or beginning graduate level class on organic free
radical chemistry, one is at a loss to find an
appropriate textbook. The book by Fossy, Lefort, and Sorba fills this void to a
certain extent. They have written a good
book on organic free radical chemistry.
The book is divided into four parts.
Part 1 contains eight chapters. This part
of the book introduces the reader to the
fundamental aspects of free radical chemistry. A brief chapter on the detection and
characterization of free radicals by electron paramagnetic resonance (EPR) and
chemically induced dynamic nuclear polarization (CIDNP) starts the text. The
next six chapters discuss the issues of radical structure, stability, reactivity, mechanisms. and kinetics. Carbon as well as heteroatom radicals are covered as part of
the discussion. Although each chapter is
quite short, enough details including
tables are included. Aspects of radical reactions are the main thrust of the second
part of the book. Chapter 9 describes different methods for generating radicals.
The important low-temperature radical
initiation method using triethylboraneoxygen is absent from this discussion. Different aspects of radical-radical and radical-molecule reactions are detailed in the
next three chapters. Radical substitution,
addition, and fragmentation reactions are
analyzed, including aspects of their regioand stereochemical outcome. Radical cyclizations and rearrangements are discussed in some detail in Chapter 13. Aro-
l4dzgsgesalischafi mhH. 0-69451 Weinheim. 1996
matic homolytic substitutions and reactivity of radical cations and anions are
discussed in Chapters 14 and 15 respectively. A short chapter on free radicals in
biochemistry is included as Chapter 16.
This section of the text ends with a discussion of different methods used to determine whether o r not a particular reaction
proceeds through a radical intermediate.
Part 3 of the book treats synthetic aspects
of organic free radical chemistry. These
include: functionalization of non-activated carbon-hydrogen bonds leading to
halogenation and hydroxylation, functional group interconversion, addition to
multiple bonds, cyclization, aromatic substitution, and coupling reactions. This
section ends with a brief discussion on the
industrial application of free radical
methods. Part 4 of the book provides references and a set of tables containing important thermochemical and kinetic data
for a variety of reactions.
This book is an ambitious project. The
authors attempt to cover all aspects of organic free radical chemistry, but sometimes these are treated only in a cursory
manner. The tables at the end are very
useful and the index is adequate. The
book could have been strengthened by a
better and more up-to-date reference section. Overall, this is a valuable addition to
any library and to the bookshelves of
practitioners of free radical chemistry.
With supplementary information from
the teacher, the book could serve as a text
for upper level undergraduate or beginning graduate level courses on organic
free radical chemistry.
Mukund P. Sibi
North Dakota State University
Fargo, N D (USA)
0570-0833196/3521-2543$ iS.O0+ .2.(,0
Без категории
Размер файла
276 Кб
curran, porte, book, reaction, radical, review, stereochemistry
Пожаловаться на содержимое документа