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Book Review Reviews in Computational Chemistry. Edited by K. B. Lipkowitz and D. B. Boyd

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acetates of 1 a and 2 a were obtained by treatment with n-butyl isocyanatoacetate in THF for 24 hr at 0°C with triethylamine catalyst. the reactions were
worked up by diluting with water and extracting with ether. Purification was
achieved by flash chromotography.
Received: September 15, 1990 [Z 4245 IE]
German version: Angew. Chem. 103 (1990) 459
CAS Registry numbers:
1 a, 132540-65-9;Za, 128141-84-4;3-carboxy-2,2,5,5-tetramethyl-2,5-dihydropyrrolyl-1-oxide, 2154-67-8; 2,4-hexadiyne-l,6-diol, 3031-68-3; 4-ethynyl2,2,b,b-tetramethyl-1,2,5,6-tetrahydropyridyl-l
-oxide, 691 16-02-5; propargyl
alcohol, 107-19-7.
[5]
[l] D. Bloor, R. R. Chance, NATO AS1 Ser. E 102 (1985) (Polydiacetylenes).
[2] a) Yu. V. Korshak, T. V. Medvedeva, A. A. Ovchinnikov, V. N. Spector.
Nature 326 (1987) 370; A. L. Buchachenko, R. P. Shibaeva, L. P. Rozenberg, A. A. Ovchinnikov Kim. Fir. 6 (1987) 773; D. J. Sandman, G. P.
Hamill, M. Levinson, P. G. Rossoni, E. A. Yost, G. C. Papaefthymiou
M R S Symp. Proc. 173 (1990) 567; J. S. Miller, D. T. Glatzhofer, R. Laversanne, S. Chittipeddi, P. Vaca, T. B. Brill, M. D. Timken, C. J. OConnor,
J. H. Zhang, J. C. Calabrese, A. J. Epstein Chem. Mater. 2 (1990) 60; b) Y
Cao, P. Wang, Z. Hu. S. Ki, L. Zhang, J. Zhao Solid State Commun. 68
(1988) 817; Syntk. Met. 27 (1988) 8625; c) D. W. Wiley, J. C. Calabrese,
J. S. Miller, J. Chem. SOC.Chem. Commun. 1989, 1523.
[3] J. S. Miller, A. J. Epstein, J. Am. Chem. Soc. 109 (1987) 3850; J. S. Miller,
A. J. Epstein, W. M. Reiff, Chem. Rev. 88 (1988) 201.
[4] a) l a : m.p. 105.5-106.5’C. Correct elemental analysis (C,H,N);
MW,,,, = 276.31 ;mass spectroscopy yielded a parent at mje 276 ( M e ) and
major peaks at 246 ( M e - CH,O) and 153. Thermal gravimetric analysis
[6]
[7]
[S]
(TGA) and differential scanning calorimetry (DSC) (10” min- ’) showed no
change until the 107°C m.p., after which a mild exotherm preceded an
endothermic weight loss of 8-9% over the range 160-190°C. At 250280”C, more rapid decomposition started with a total weight loss of 50%
by 350°C. b) 2a: mp 119.3-120.1 “C. 2 a is completely stable in the solid
state, but darkens slowly and loses its free radical characteristics when
dissolved in organic solvents. Correct elemental analysis (C,H,N);
MW,,,,. = 232.30; mass spectroscopy yielded a parent at mje 232 ( M e ) and
202 ( M e -CH,O). TGA and DSC (10” min-’) showed no change until the
117-121°C mp, after which a sharp exotherm occurred. Small samples
showed a slow weight loss of 3-5% up to 170°C. where larger samples lost
up to 60% of their weight already at 140°C. This behavior reflects a weight
loss owing to a sputtering of material out of the measuring cup.
A 0.25 x 0.15 x 0.36 mm crystal was grown from MeOH/H,O: orthorhombic P2,2,2,(No. 19) space group; a = 8.217(2), b = 10.465(2), c =
17.119(2)A; V = 1472.1 A3; 2 = 4; p..,.. = 1.247 g/cm3; pMo,0.85 cm-’ at
- 60 ”C. Enraf-Nonius CAD4 diffractometer; graphite-monochromated
Mo,, radiation; 3923 reflections. Refinement: 1285 reflections for which
I > 20(0 to convergence of R = 0.047 and R, = 0.039. See also 171.
A 0.35 x 0.21 x 0.43 mm crystal was grown from warm 40% aqueous
MeOH: monoclinic P2Jn (No. 14) space group; a = 5.784(2),
b = 22.158(3), c = 10.541(3)A; = 104.05(1)”; V = 1310.5 A3; 2 = 4;
= l.177gcm-3;pMQ,
0.73cm-Iat -70°C. Enraf-NoniusCAD4diffractometer; graphite-monochromated Mo,, radiation; 3249 reflections.
Refinement which 1513 reflections for which I > 3a(I) to convergence of
R = 0.051 and R, = 0.051. See also [7].
Further details of the crystal structure investigation are available upon
request from the Director of the Cambridge Crystallographic Data Centre,
University Chemical Laboratory, Lensfield Road, GB-Cambridge CB2
1EW (UK), on quoting the full journal citation.
R. Baughman, R. R. Chance, Ann. N.Y. Acad. Sci. 313 (1985) 705.
BOOK REVIEWS
Book Reviews are written by invitation from the
editor. Suggestions for books to be reviewed and
for book reviewers are welcome. Publishersshould
send brochures or (better) books to the following
address: Redaktion Angewandte Chemie, Postfach 101161, D-6W Weinheim, Federal Republic
of Germany. The editor reserves the right of selecting which books will be reviewed. Uninvited books
not chosen for review will not be returned.
Reviews in Computational Chemistry. Edited by K . B. Lipkowitz and D . B. Boyd. VCH Publishers, New YorkJVCH
Verlagsgesellschaft, Weinheim 1990. xix, 419 pp., hardcover, DM 176.00.-ISBN 0-89573-754-X/3-527-27845-1
In the introduction to this book the editors try to arrive at
a definition of “computational chemistry”. According to the
broadest of the definitions offered here, it includes all those
areas of chemical research in which computers are used
452
0 VCH
Verlagsgesellschafr mbH, W-6940 Weinheim. 1991
either to obtain results more quickly or to make the work
possible at all. On this criterion there is nowadays scarcely
a single area of chemical research that does not overlap with
computational chemistry. The present volume is intended as
the first of a series that will follow, by means of review
articles, the development of every aspect of computational
chemistry, including molecular modeling. It can be stated at
the outset that the editors have succeeded here in presenting
some excellent articles on topics of current interest in the
field of computer applications in chemistry.
The first and last chapters in the book are both concerned
with ab initio quantum chemistry. In the first of these, on
“Basis Sets for Ab Initio Molecular Orbital Calculations and
Intermolecular Interactions”, D . Feller and E. R. Davidson
describe basic principles and recent developments in this
area; they include a section entitled “In-Depth Discussion”,
which well deserves this description. There is a useful table
listing the polarization functions in common use, information which would be hard to find elsewhere.
In the second chapter J. J. P. Stewart discusses semiempirical methods. The rather bewildering array of methods originating from the Dewar school that have been developed in
the last few years (MNDO, MNDOC, AM1, PM3, etc.) are
described in chronological order. The theoretical fundamentals are only treated very briefly. The author justifies this by
+
0570-0833/91/0404-0452$3.50 .25/0
Angew. Ckem. Int. Ed. Engl. 30 (1991) No. 4
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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