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Book Review Chemistry of Plant Protection. Vol. 4 Synthetic Pyrethroid Insecticides. By K. Naumann

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referring to a recent review article on this topic by W. Thiel,
commenting that to attempt to cover the same ground here
would merely result in repetition-an admirable example of
self-restraint! Although the account of the areas of application of the methods contains some slight inaccuracies-for
example, it is wrongly stated on page 62 that for MIND0/3
no parameters for the P - 0 bond are available-these do not
detract from the value of this fluently written article. The
detailed survey, in the form of a table, of the average errors
with the three main methods (MNDO, AM1 and PM3) for
several classes of compounds is a very useful guide for the
potential user.
In the third chapter (“Properties of Molecules by Direct
Calculation”) C. E. Dykstra, J. D . Augspurger, B. Kirtman
and D . J. Malik address the question of which are the most
suitable theoretical methods for directly calculating properties from the wave functions. They limit their discussion to
the calculation of electrical, magnetic and optical properties,
force constants and transition probabilities. The article is
worth reading as an introduction and a concise account of
the basic mathematics, but the discussion of the results, consisting of a mere nine pages, is too brief for such an extensive
topic.
Four chapters are devoted to the subjects of molecular
modeling and quantitative structure-activity relationships.
This is appropriate and welcome in view of the rapid developments taking place in this area and the shortage of review
articles. For this strongly applications-orientated area of
computational chemistry it is also fitting that three of the
four articles have been written by authors from industry.
D . B. Boyd introduces this topic in Chapter 9 (“Aspects of
Molecular Modeling”), where he discusses the usefulness of
the different theoretical approaches from the viewpoint of
the industrial chemist dealing with large molecules. The fact
that molecular modeling is very far from being an “amateurish, watered-down, or incidental computational chemistry”
(p. 321) is made clear by E. L . Plummer in Chapter 4 (“The
Application of Quantitative Design Strategies in Pesticide
Discovery”). This detailed article (49 pages) describes the
application of theoretical aids, especially statistical methods,
to synthetic and analytical strategies in the search for new
pesticides compatible with present-day restrictions (ecological requirements). It has been known for some time that in
order to realistically model the properties of large molecules
one must take into account their dynamic behavior. The
development of the three main approaches, namely Monte
Carlo methods, molecular dynamics calculations, and the
calculation of the free energy using perturbation theory, is
sketched rather briefly (in 25 pages) by 7: P . Lybrand in
Chapter 8. The practical usefulness of computational chemistry is illustrated by D. B. Boyd in Chapter 9 by taking as
examples four commercial compounds whose development
depended crucially on computer-aided methods.
The importance to analytical chemistry of computers and
of the multivariate analysis methods that are thereby possible is described in Chapter 5 (“Chemometrics and Multivariate Analysis in Analytical Chemistry”, 43 pp.) by P. C.
Jurs. This chapter too can be regarded as belonging to the
area of molecular modeling in the wider sense, since the main
emphasis is on applications concerning structure-activity relationships for biologically active substances.
The development of computer graphics, which allows one
to quickly and conveniently display three-dimensional structures on the VDU screen, is of enormous significance for
chemistry. The influence that this is having on the development of modern data banks, which allow one to rapidly test
ideas about molecular structures using stored three-dimenAngew. Chrm. Int. Ed. Engl. 30 (1991) No. 4
0 VCH
sional information, is described in Chapter 6 (“Searching
Databases of Three-Dimensional Structures”, 51 pp.) by
E: C. Martin, M . G . Bures and P. Willet. Whereas older data
banks such as the Cambridge Structural Database are used
essentially for storing data on atomic coordinates, the newer
types of programs allow one to search for information about
specific partial structures. References to available programs
and information sources are included in this detailed report.
Advances in computer graphics have also contributed significantly to the development of concepts in which one is
mainly interested in the molecular surface. In Chapter 7
(“Molecular Surfaces”, 30 pp.) P. G. Mezeji reviews theoretical models in which molecular properties are correlated with
the shape of the surface. One such model is that developed by
M . L. Connolly to describe the surface accessible to a solvent; this has contributed to a better understanding of solvent effects on proteins. It becomes clear from the article that
this new concept would scarcely have been possible without
the development of computer graphics.
The final chapter (“Perspectives on Ab Initio Calculations” by E. R . Davidson) is not concerned with the practical
details of the development of ab initio methods but with the
question of what can be learned, and has already been
learned, by using ab initio programs. The author’s personal
views, supported by historical examples, are briefly set out
under five headings; everyone will undoubtedly agree with
the last of these headings, which asserts that “Computers do
not Solve Problems, People do”.
The book contains as an appendix a survey by D. B. Boyd
of hardware and software relevant to molecular modeling
(together with details of suppliers); this is prefaced by a
useful and amusing checklist of points about which one
needs to be clear before buying a computer or software.
The standard of production of the book is excellent, there
are few printing errors, and the price seems reasonable in
relation to the levels that are now typical. It can be recommended for everyone who wants to learn about the present
state of development in computational chemistry, and is willing to look beyond the boundaries of his or her particular
field of study. Specialists will need to decide for themselves
whether the chapters of particular interest to them offer
something new. Libraries of chemistry departments are
strongly recommended to buy the book. The choice of topics
is certainly subjective, but is sensible and relevant to current
developments in computational chemistry. It is to be hoped
that further volumes of the series will appear at intervals of,
say, two years. The editors can be congratulated on this first
volume.
Gernot Frenking INB 111 3 IE]
Fachbereich Chemie
der Universitat Marburg (FRG)
Chemistry of Plant Protection. Vol. 4: Synthetic Pyrethroid
Insecticides. By K. Naurnann. Springer, Berlin 1990. xvi,
241 pp., hardcover, DM 224.00.-ISBN 3-540-5131 3-2
The series “Chemistry of Plant Protection” is the successor to the well-known handbook “Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel” by R. Wegler. It
is not only the language that has altered, there has also been
a change in the editorial policy. Whereas the Wegler handbook follows a conventional division of subject matter, dealing in turn with herbicides, fungicides and insecticides, the
volumes of this series will deal with individual topics of current importance. Thus Volume l is devoted to the inhibition
of sterol biosynthesis, Volume 2 to the biological breakdown
Verlagsgeseilschaft mbH, W-6940 Weinheim. 1991
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OS70-0833/91jO404-04S3 $3.50 ,2510
453
of pesticides, the defoliation and dessication of green plants,
and methods of influencing acetylcholine receptors, and Volume 3 to the detection of pyrethroid residues and the measurement of active substances of low molecular mass by immunoassay. With Volumes 4 and 5, which take pyrethroids
as their common central theme, the editors now face the risk
of breaking down the subject into too many individual topics. Volume 4 deals with the structures and biological activities of the most important pyrethroids, while Volume 5 (in
preparation) will describe their synthesis and chemical properties.
Volume 4 begins with a brief historical account of the
development of the synthetic pyrethroids based on the natural pyrethrins; the latter still play an important role in human hygiene (lice etc.), although they are unsuitable for
plant protection uses because of their photolability. Many
modern pyrethroids bear only a marginal resemblance to the
natural pyrethrins; in some cases the only indispensable
structural element that is retained is the geminal carbon
branching, which acts as a lipophilic anchor. The author
identifies the structural characteristics that need to be present in a “good” pyrethroid, and includes extensive tables
describing the structure-activity relationships. It is interesting that the (IR) enantiomers are found to have the highest
activities. With regard to the cisltrans-I ,2-substitution of the
cyclopropane ring or at the double bond the diastereomers
show characteristic differences in their activities; which of
the stereoisomers has the highest activity depends very
markedly on the substitution pattern and the insect target
group. However, the alcohol component of the cyclopropanecarboxylic acid ester also has a crucial effect; a phenoxyether has the effect of causing the molecule to adopt the
important “horseshoe” conformation (pp. 76 f).
About 80 pages are devoted to the biological effects of
pyrethroids on insects and other forms of life. Nearly all
insect species suffer physiological effects from pyrethroids.
After absorption through the cuticulum (contact toxicity!)
the substance produces the immediate “knock-down’’ effect,
which may or may not be followed by death. In this respect
it is possible to obtain some discrimination between harmful
insects and those that are useful; useful insects such as bees
can recover from the initial “knock-down”, whereas harmful
insects are killed. However, a serious drawback of nearly all
pyrethroids is their high level of toxicity towards marine life
(fishes, leeches etc.), which prevents their use in rice-fields.
Pyrethroids are essentially harmless to warm-blooded species, although they cause unpleasant skin irritations in humans, which nevertheless quickly clear up. In insects, in contrast to warm-blooded species, pyrethroids rapidly penetrate
into the nerve fibers, where they open up presynaptic sodium
channels and thereby disrupt the entire nervous system. In
warm-blooded species the pyrethroid molecules first undergo ester hydrolysis and hydroxylation which destroys the
activity.
The final chapter discusses the market share enjoyed by
pyrethroids (currently about 20%) and the areas of use. In
addition there is a comprehensive list of the various derivatives, including not only the usual commercial products but
also those still at the development or experimental stage,
together with manufacturers and licensees.
On the whole this is an excellent book. No important
aspect of the subject appears to have been overlooked; the
factual information is supplemented by extensive numerical
tables that have been carefully prepared. A possible criticism
is that the environmental acceptability of the pyrethroids is
only briefly discussed. For example, there is very little information (six lines on p. 124) about the biological degradation
of the insecticides on cultivated land, and the avoidance of
harm to useful insects is undoubtedly a serious problem. A
minor detail that can be criticized is the frequent use of trivial
names (deltamethrin, permethrin etc.) without giving the
reader quick access to the structural formulas. It is only
when one reaches page 192 that one finds, without an earlier
reference to it, a table giving such information, and even here
the compounds are not arranged alphabetically. However,
these relatively minor criticisms scarcely detract from the
favorable overall impression. The book is undoubtedly a
must for everyone working in the area of pyrethroids, whether
as a chemist, biologist, pharmacologist or toxicologist.
Johann Mulzer [NB 11 26 IE]
Institut fur Organische Chemie
der Freien Universitat Berlin (FRG)
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Angew. Chem.Inr. Ed. Engi. 30 (1991)No. 4
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