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Integrated Chemical Processes. Synthesis Operation Analysis and Control

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Metallocenes in Regio- and
Stereoselective Synthesis
Series: Topics in
Chemistry, Vol. 8.
Edited by Tamotsu
Takahashi. Springer
Verlag, Heidelberg
2005. 244 pp.,
E 176.50.—ISBN
This book is the eighth volume in the
series Topics in Organometallic Chemistry, and consists of six chapters written
by leading experts in metallocene
chemistry. Although most of the chapters deal with the metallocene complexes of early transition metals such
as Zr and Ti, some recent topics on work
using late transition metals are also
included. The references in all of the
chapters extend up to the year 2002.
Each chapter has a general introduction
to the respective area of research, which
may help beginners to understand the
basics, although this book is aimed at
specialists who wish to have an up-todate summary of recent developments
in this field.
In the first chapter, “Hydrozirconation and its Applications”, P. Wipf and
C. Kendall review the recent examples
of hydrozirconation and its application
to natural products synthesis, focusing
on the development of this subject since
1996, when their last comprehensive
review appeared. As well as describing
a general method for the preparation of
Schwartz reagent, the chapter covers the
synthesis of alkyl- or alkenylzirconium
reagents by the hydrozirconation of
Angew. Chem. Int. Ed. 2005, 44, 6807 – 6808
alkenes and alkynes. Even more importantly, the authors give a good summary
of the synthetic application of organozirconium reagents for the formation of
carbon–carbon and carbon–heteroatom
bonds, including especially the novel
cross-coupling reaction utilizing transmetalation with late transition metals.
The second chapter, “Construction
of Carbocycles via Zirconacycles and
Titanacycles”, by Z. Xi and Z. Li,
describes the preparation of metallacyclic intermediates and their application
to the synthesis of carbocyclic compounds. Most of the chapter is concerned with zirconocene- and titanocene-mediated reactions for the preparation of three- to nine-membered carbocycles.
The third chapter, “MetalloceneCatalyzed Selective Reactions”, by M.
Kotora, gives a brief overview of recent
developments in catalytic organic reactions using cyclopentadienyl metal complexes of both early transition metals
and late transition metals such as Fe, Ru,
Co, Rh, and Ir. The reactions are
classified into seven types. A plausible
reaction mechanism is described and
shown schematically, which helps readers to understand the course of the
E. Negishi and Z. Tan, in the chapter
entitled “Diastereoselective, Enantioselective, and Regioselective Carboalumination Reactions Catalyzed by Zirconocene Derivatives”, describe a highly
selective carboalumination and its application to the synthesis of some natural
products. After a general discussion of
the carbometalation method that has
been developed by the authors, they
give an excellent summary of the application of the zirconium-catalyzed carboalumination of alkenes to the stereoselective synthesis of natural products.
In particular, the asymmetric carboalumination described in this chapter is
useful for obtaining key intermediates
towards natural products.
The following chapter, by N. Suzuki,
is entitled “Stereospecific Olefin Polymerization Catalyzed by Metallocene
Complexes”. The author discusses the
polymerization of propylene, styrene,
methyl methacrylate, 1,3-dienes, nonconjugated dienes, and cyclo-olefins,
focusing on recent examples of the
synthesis of stereoregular polymers.
The last chapter is a review by T.
Takahashi (the volume editor) and K.
Kanno. Under the title “Carbon-Carbon
Bond Cleavage Reaction Using Metallocenes”, the authors discuss stoichiometric reactions involving C C bond
cleavage using metallocene complexes,
and focus on the understanding of these
reaction mechanisms. The C C bond
cleavage reactions are classified into
three types according to the bond
order of the C C bond.
In summary, this book presents valuable information on recent topics in
metallocene chemistry, especially on the
stereoselective synthesis of organic compounds. The book is definitely valuable
for a quick understanding of this field,
and also quite useful to the specialists in
this area.
Takahiro Nishimura
Department of Chemistry, Graduate
School of Science
Kyoto University (Japan)
Integrated Chemical Processes
Synthesis, Operation, Analysis, and
Control. Edited by
Kai Sundmacher,
Achim Kienle, and
Andreas Seidel-Morgenstern. WileyVCH, Weinheim
2005. 540 S., hardcover, 199.00 E.—
ISBN 3-527-30831-8
This book aims to show how one can
simplify the sequence of operations in
an industrial chemical reaction process,
and improve its efficiency, by integrating
techniques (and even new reactors and
reactor components) together. This concept has become known as the “taskintegrated technique”, which is defined
as different techniques integrated within
a single piece of equipment. It is often
illustrated by referring to the example of
a reactive distillation process.
8 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
In this book, the concept is broadened, as indicated by the title Integrated
Chemical Processes. This is to be understood as the integration of basic operations that may be widely different, thus
resulting in a “multifunctional” process,
which offers the possibility of higher
productivity and selectivity, more efficient energy use, greater inherent safety,
and a reduction in environmental
impact. The task of designing such processes should be guided not only by the
aim of “process intensification”, but also
by considerations of “sustainable development” and the view that there is a
need to move towards “green chemistry”. That is a formidable task, and the
book by Sundmacher, Kienle, and
Seidel-Morgenstern must be judged
according to how convincingly it
explains the possibilities.
The book divides the task into three
parts, according to the different processes and operations to be integrated
together in a chemical reaction: heat
transfer processes (Part I), thermal separation operations (Part II), and
mechanical separation operations (Part
III). Thus, the challenge to be overcome
involves much more than a comparatively simple “task integration”, and it
can also be separated into the integration of unit operations and that of unit
processes into chemical reactions (which
are to be understood essentially as
chemical “processes” in this book).
The unit operations to be considered
include the heat-transfer processes
already mentioned, as well as adsorption, absorption, and hydrodynamics,
whereas unit processes include thermal
separation processes such as distillation,
and the mechanical processes for separation, comminution, and particle conditioning, by techniques such as milling,
crystallization, filtration, or granulation.
Within this classification, the book has
separate chapters on combined heat and
charge transport (Chapter 3), the equilibrium theory of nonlinear waves
(Chapter 5), reactions at membranes
(Chapter 12), and the simulation of
moving-bed reactors (Chapter 6).
The basic chapters, such as the
introductory chapter on “Integration of
Heat Transfer and Chemical Reactions”, and the articles on “Thermodynamic and Kinetic Effects on the Feasible Products of Reactive Distillation”
and on “Structured Catalytic Reactors:
Hydrodynamics and Reaction Performance”, are further subdivided within
themselves, and are of high quality and
didactical value. In contrast to reviews
of the published literature in journals,
the presentation of the fundamentals is
more thorough and systematic. This is a
great merit of the book, and is a
common thread throughout nearly all
the chapters. The same also applies to
the chapters on adsorptive reactors
(Chapter 7), reactive absorption (Chapter 9), extraction (Chapter 10), and
crystallization (Chapter 11).
The chapters in Part III of the book,
on the integration of mechanical unit
processes, are mainly of more interest to
process technologists than to chemists,
but nevertheless they provide good
insights into aspects of chemical processes that are rarely in the foreground.
By reading these one can learn about
interesting innovations and potential
applications, and that is one of the
surprising benefits of the book.
The editors do not explain how they
have chosen and arranged the topics.
However, Chapters 2 and 3 on fuel cells
give a good indication of the system
followed in Part I, although it would
have been at least as useful to include a
chapter devoted to the practical applications of reactive distillation and to
describing commercial processes (a possibility hinted at in Chapter 1 by Eigenberger et al.). The chapters on movingbed simulations (Chapter 6) and on
catalytic membrane reactors (Chapter
12) can also be regarded as typical
examples, although it is not quite clear
why these were chosen. However, some
inconsistencies can be explained on the
ground that the book is a collection of
articles from a Max-Planck symposium
in 2004, which may explain the fact that
some parts of the book lack chapters
8 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
that would have linked topics together
and given a more systematic impression.
The subject of Chapter 5, the
dynamics of nonlinear waves, has applications to the analysis of reactive distillation processes and to chromatographic reactors, but the example of
the separation of binaphthol enantiomers is rather exotic, leading one to
suspect that the authors of this chapter
have chosen a familiar and favorite
example (perhaps the only available
The book certainly fulfills its aim of
explaining the advantages of an integrated combination of reactions and
processes and the bringing together of
unit operations and unit processes. It is
probably as comprehensive, didactic,
and rich in examples as is possible at
the present time, and therefore it lives
up to the promise on the dustcover: “…
the first book dedicated to the entire
field …”. However, I have serious
doubts about the criteria of sustainable
development and the aim towards
“green chemistry” that are implied in
the preface. There, in a brief history of
the subject, the editors describe the
developments in this area as very logical
and consistent with the best traditions of
chemical and chemical engineering
research, and claim that they are
always (!) directed towards “unpolitical” improvements in yield and selectivity, simplification of plant requirements,
and increased efficiency of processes.
Such developments are possibly
(although not necessarily) categorized
as “sustainable” and “green”, but one
would be doing an injustice to entire
generations of researchers to describe
sustainability and green chemistry as
brand-new objectives (and brand-new
Boy Cornils
Hofheim/Taunus (Germany)
DOI: 10.1002/anie.200585323
Angew. Chem. Int. Ed. 2005, 44, 6807 – 6808
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integrated, synthesis, chemical, processes, operation, analysis, control
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