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Book Review Modern Electroorganic Chemistry. By D. Kyriacou

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BOOKS
A Nucleus of Modern Chemical Techniques
Adkanced Organic Chemistry of Nucleic Acids. By Z . A ShLihutvva and
A . A . Bogrlmov. VCH Verlagsgesellschatt. Weinheim, 1994. 588 pp.,
hardcover DM 248.00. --ISBN 3-5272902 1-4
Alungsidc the classical disciplines of organic. inorganic, and physical chemistry,
a number of related disciplines are nowadays increasing in
importance. One of
these is bioorganic
chemistry. Whereas
it was formerly regarded a s just a
minor branch of bi<)logy.or ;tt best accepted a s biocheniistry and perhaps
tolerated at the periphery of organic
chemistry. this field is now. with good reason. being wen its increasingly important.
The growth of interest in this interdiscipliixiry area is gaining further momentum
from the rapid adbances in research into
the in olecul ;I r inechan i sins that determine
life. In particular the developments i n
protein and nucleic acid chemistry are the
pacemakerh.
During thc last few years several monographs dealing with these topics at a specialist l e ~ e lhave appeared. In contrast.
the cuistin~textbooks are not up-to-date.
The book reviewed here. by the Russian
authors Zoe Shabarova and Alexey Bogdanov. is the most recent treatment of nucleic acid chemistrq. As indicated by the
title. the sub-ject of the book is the organic
chemistry 01' this class of natural compounds. In t l i t preface the authors make it
clear that their main aim was to produce a
textbook specifically for students.
The book is a completely revised English version of the textbook originally
published by the same authors in 1978 in
Russian under the title "The chemistry of
Nucleic Acids and their Compounds".
Much new material has been added, including a chapter on the highly topical
subject of ribozymes.
The book is divided into 1 1 chapters
(588 pages), most of which have been
written by Z. Shabarova. First the structure of nucleosides is described (Chapter 1 : pyrimidines and purines, importance of the configuration of the anomeric center. nucleoside antibiotics).
Their properties are then discussed
(Chapter 2: tautonieric structures. reactions with nucleophiles and electrophiles.
addition reactions. stability of the glycosidic bond). The following chapters describe the nucleotides which are the building blocks of DNA and RNA (Chapters 3
and 4: acidibase behavior, properties of
the phosphate group(s), reactions at
the phosphate group). Beginning on
page 187. Chapter 5 deals with the priniary structure of the nucleic acids DNA and
RNA. The nomenclature of nucleic acids
is explained. followed by a discussion of
the action of nucleases and methods for
determining the nucleoside sequence. In
Chapter 6 ("Determination of the Primary Structure of Nucleic Acids") the methods of sequencing are treated in greater
detail. including DNA-mapping. chemical sequencing. and enzymatic sequencing. Also included here is the method of
sequencing on a solid support. as well a s
the highly topical polymerase chain reaction (PCR) method. Chapter 7 deals u'ith
the basic features of the secondary structure of nucleic acids, including the conformational characteristics of nucleotide
monomers and single-strand oligonucleotides. The macromolecular structure of
D N A and RNA, starting with the WatsonPCrick model, is treated in Chapter 8.
Supercoiled DNA and other unusual
DNA structures such a s G-tetrads and
"hairpins" are described. followed by the
secondary structures of the t-RNAs and
high molecular mass RNAs. In the following chapter the student is introduced to
the chemical properties of polynucleotides
and to modifications of nucleic acids, e.g..
involving the carbohydrate or aglycon
moieties. The chapter ends with short descriptions of two studies of conformationa1 changes in D N A and four-stranded G4DNA. As mentioned earlier. Chapter 10
deals with the highly topical field of
ribozyme chemistry, This very readable
book ends with a chapter on a very
"chemical" aspect : the synthesis of nucleic acids. This consists of about 100 pages
in which not only chemo-emymatic methods but also the different chemical strategies of oligonucleotide synthesis are discussed in detail. The chapter is completed
by a description of the preparation of synthetic genes and the technique of cloning.
Literature references are listed at the end
of each chapter.
After reading this well-wi-itten book nobody can really doubt that the chemistry
of nucleosides and nuclcic acids is an intrinsic part of organic chemistry. Although some of the formula schemes are
unconventional and takc a little time to
get used to, the authors are to be congratulated on the quality of their work. As it
textbook this is ;I very huccessful effort.
My only complaint is that the publishers
need to introduce a cheaper paperback
version as soon 21s possible. because the
price of DM 248 is not affordable to students. I fear that until that is remedied, the
high price will limit the distribution ofthis
excellent book.
Chris Mi4c.r.
Institut fiir Organische Chemie
der Universitiit Frankfurt (Germany)
Modern Electroorganic Chemistry.
By D. Kj?r.iucou. Springer, Heidelberg,
1994. 228 pp., hardcover
DM 98.00.--ISBN 3-540-57504-9
During the last twent). years there have
been enormous developments in electroorganic chemistry and inany books
and review articles have appeared. In this
book D. Kyriacou has aimed to give a
systematic presentation of'current knowledge in the area of electroorganic chemistry. There are five chapkrs: a n introduction (17 pp.). followed by chapters on
BOOKS
anodic, cathodic. and indirect electroorganic reactions (92, 56. and 26 pp. respectively), and finally a chapter on various interesting special areas of electrosynthesis (33 pp.).
The introductory chapter presents the
fundamental principles needed for an understanding of electroorganic reactions.
The basic components required to achieve
a successful electrochemical reduction or
oxidation are described (the electrodes,
the electrolytic cell. the conducting electrolyte. and the potentiostat). and the author explains concepts such as direct and
indirect electrochemical reactions. electron transfer, electrode potential. equilibrium potential, and overvoltage.
The anodic reactions discussed in
Chapter 2 include oxidation of hydrocarbons, alcohols, phenols, carboxylic acids.
amines. amides, ethers, esters. N-heterocycles. and organosulfur compounds.
Thus, for example, the author describes
the oxidation of alkanes in the presence of
acetonitrile (acetamidation). the anodic
coupling of arenes, the Kolbe synthesis for
preparing w.w’-disubstituted alkanes. and
the synthesis of poly(2.6-dimethyl-I ,4phenyleneoxide) from 2,6-dimethylphenol. The anodic substitution reactions described include cyanidation, acetoxylation. halogenation. hydroxylation, and
alkoxylation.
The cathodic reactions discussed in
Chapter 3 are electrochemical hydrogenations and reductions of carbonyl. organohalogen, organonitro, and organosulfur
compounds and of N-heterocycles. and
also electrocarboxylation. Thus, for example. cyclopropanes are synthesized
from alkenes in the presence of methylene
bromide at a graphite cathode. which is
combined with a zinc sacrificial anode in
an unpartitioned cell. The reduction and
hydrolysis of purine gives 4-aminomethyl5-amino-2-imidazoline, and the electrocarboxylation of ethene gives succinic
acid. Carbon dioxide is converted to
methanol in a photoelectrochemical reduction using leuco-indigo. and the indigo
thus generated is then reduced back to
leuco-indigo. The latter process forms the
basis of a recently developed solar cell.
In cases where the electron exchange in
an electrochemical oxidation takes place
via a mediator the reaction is said to be
indirect. Chapter 4 deals with indirect
electroorganic reactions, under the headings of oxidative and reductive indirect reactions. Species that can be used as oxidative mediators are the transition metal
ions C e S + and R u 4 + . the halogen cations
I + and Br’, and tris(p-bromopheny1)amine. Metal ions in low oxidation states.
such as Fe2+. Cr”. and Sn” , are effec-
tive as reductive mediators. Anthracene is
used a s an organic reductive mediator.
The final chapter collects together a
number of special areas of electroorganic
synthesis. such as electropolymerization
and the synthesis of natural products.
This book covers all the important
modern developments in electroorganic
synthesis, and by providing a wealth of
literature references enables the reader to
study this interesting field in greater
depth. The inclusion of laboratory recipes
for the electrochemical synthesis of many
different compounds is especially useful.
Moreover, all the information in the book
is very clearly presented. There are few
errors, and those that have occurred d o
not detract from the very high quality of
the book. For example, it was undesirable
to use the same symbol Q for quantity of
charge (p. 14) and for the quotient of the
activities in the Nernst equation (p. 8).
For consistency the formula chosen for
naphthalene on page 95. with five double
bonds (ten rc-electrons). should also have
been used on page 21.
Kurhiii: Sc>!fiW
Lehrstuhl fur Organische Chemie I/2
der Universitiit Bayreuth (Germany)
Derivative Spectrophotometry. Low
and Higher Order. By G. Tulsky. VCH
Verlagsgesellschaft, Weinheim, 1 994.
228 pp., hardcover DM 248.00.ISBN 3-527-28294-7
I approached this book with high expectations, hoping to learn about important applications of derivative methods to
spectroscopic interpretation. However,
my first impressions were that the publishers had not made a very good job of language-polishing, and also that the text
ought have been checked by a proof-reader with a mathematical background. For
me there were many small points that rankled. The impression is given that the infrared region ends at 2.5 pm. thus:
“Higher energies are necessary though.
for electron excitation.” Sometimes things
are expressed in an awkward way, as in
*‘...the curve is computet”, or “...derivative orders contribute only littel ...” In
stating the Lambert-Beer law the mention of Bouguer as the earlier discoverer is
wrongly spelt, and Volkmann is wrongly
cited as the author of a book on “infrared
spectrophotometry”. These printing errors are mildly amusing. but the mistakes
in the mathematical formulas are pure
carelessness, and several times I had to
overcome a strong temptation to abandon
the book. Sometimes plus signs, sub- and
superscripts are missing. while in other
cases a symbol that shoutd be a subscript
is printed at normal height. Occasionally
the wrong result is given for an elementary
operation such as differentiation or calculation of a logarithm-. sorry. such mistakes just cannot be tolerated. Proportional is not the same as equals!
The chapter on derivatives, for example
those of the Gaussian function, is unnecessarily awkward and labored. I cannot
understand why the author has not kept
to a consistent nomenclature (there was
already a hint of this in the discussion of
the various symbols for differentiation).
It seems a little strange that extinction coefficients and band distances are given in
millimeters. And since when is the
Lorentzian band-shape an exponential
function? The Savitzky - Golay smoothing equation (Eq. 3-22) contains printing
errors. Certain general recursion formulas
are cited without mentioning the restrictions stated in the original publications.
I was often reminded of old times when
the author referred to cutting out peaks
and weighing to determine their areas,
and again in the descriptions of instrumentation. Even graphical methods of estimating tangents are included. The Iiterature references too are a little antiquated.
What is the purpose of the short digression on the binary system‘?-It is hardly
necessary to point out that modern computers still use it. I certainly did not think
that analog and hybrid methods still have
an important role in differentiation routines. The literature on digital methods of
smoothing and differentiation is well covered. However, references to some recent
monographs on this subject area should
certainly have been included (e.g., P.
Gans, Dritu Fitting in the Cheniical
Sciences, Wiley, Chichester, 1992). One
would also expect to find a mention of
recent publications on the suppression or
elimination of “spikes”.
The treatment of practical aspects begins with Chapter 4. However, the choice
of examples to illustrate the advantages of
derivative spectroscopy seems to me unconvincing. With regard to the fundamental question of what is the optimal order
of differentiation, the author’s answer is
that every shoulder and turning point in
the original spectrum must appear in the
derivative as an extreme value. It would
also have been useful to compare the
derivative method with alternative procedures that have grown in importance in
the last few years, for example resolution
enhancement using techniques such as the
maximum entropy method or self-deconvolution; these avoid the interference by
satellites that can arise in derivative spec-
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