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Preparative chemistry using supported reagents
Reactive Polymers, 10 (1989) 89-93
89
Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands
BOOK REVIEWS Publisher's Note: The Publisher received two different reviews of the book Preparative Chemistry Using Supported Reagents. Both are presented below.
Preparative Chem&try Using Supported Reagents, by Pierre Laszlo (Ed.), Academic Press, San Diego, 1987, xiv + 545 pages, ISBN 0-12-437105-1, $110.00.
This book, edited by Pierre Laszlo, contains 27 chapters written by experts in the field. To a practitioner of polymer-supported chemistry, Laszlo's introduction comes as a surprise, as almost no mention is made of polymers. Laszlo traces the origins of the field to heterogeneous catalysis and chromatography, both on inorganic supports, then mentions briefly the example of biochemistry where enzymes provide an ideal model of supramolecular chemistry applicable to the design of new polymer-supported reagents or catalysts. Though Merrifield's solid-phase synthesis and supported enzyme techniques are mentioned in cursory fashion, ion-exchange resins and supported cells are not. In fact, this apparent omission is not inappropriate in the context of a book which has chosen as its main focus chemistry on inorganic supports. Supported reagents based on organic supports are mentioned only very briefly in three chapters, which can only manage to provide a flavor of the field of polymer-supported chemistry. A great strength of the book can be traced to Laszlo's judicious choice of several introductory chapters, which expose various principles of chemistry on solid surfaces that are clearly germane to all supported reactions and add greatly to the overall usefulness of the book.
Thus, in chapter two, Pfeifer offers a concise overview of the principles of fractal surface characterization; this is of great importance to the design of supported reagents and many practitioners in the field of supported chemistry will greatly benefit from reading it. Other early chapters provide insight in the photochemistry of adsorbed molecules and electrochemical synthesis at modified electrode surfaces. Several interesting chapters are devoted to the development and use of physico-chemical methods and tools for the study of surfaces or supported reagents in general. A most useful chapter written by Corn~lis contains a first-hand account of several practical recipes and numerous useful hints for anyone who might wish to set up a reagent supported on inorganic supports such as clay or silica. As mentioned earlier, three individual reviews concerned with polymer-supported chemistry follow, but these are of such limited scope that they can only provide a very fragmentary view of what has been done, or what could be done, using organic supports. Perhaps these chapters should not have been included at all in this book as they do not blend well with the rest of the text. A second strength of the book is its excellent coverage of reagents supported on inorganic materials. This coverage is semi-encyclopedic, covering most of the known applications of reagents based on inorganic supports, with generous references extending to mid-1985. Individual chapters cover the following supports: metal oxides, graphite, alumina, silica, zeolites and clay.
90
Unfortunately perhaps not all chapters include a critical perspective of the field, or suggest future directions. Particularly interesting in this context is Posner's enlightening writing on alumina-supported reagents, or Csicery and Laszlo's crisp account of shapeselective catalysis on zeolites. Overall, this book will be a valuable addition to many synthetic chemists' personal library, as it brings together expertly written, if somewhat concise, reviews of topics which have seldom been considered as a whole. It will not be a primary reference to those concerned with organic reactive polymers, but it will certainly contribute to the development of new and exciting supported chemistry through increased awareness of the variety of supports which are available, their characterization and their uses. JEAN M.J. FRI~CHET
Cornell University
This text of 545 pages is a little unusual because it comprises 27 chapters, each with its own author or authors. On average therefore each contribution is only of about 20 pages. To give the book some overall structure the editor has divided it into eight parts: I. Supported Reagents: General principles II. Physico-Chemical Studies of the Structure of the Solid Supports III. Polymer-supported Reagents IV. Graphite Intercalation Compounds V. Alumina-supported Reagents VI. Silica-supported and Silica-gel-supported Reagents VII. Use of Zeolites and Supports VIII. Clay-activated Organic Reactions The book concentrates primarily on inorganic supports--alumina, silica, zeolites and clays--and deals with polymer-supported systems relatively briefly in only 60 pages--Part III, Chapter 12, 13, and 14. As a
result the text does not overlap unduly with the more specialised texts on polymer-supported species, but rather it complements these quite nicely. Part I is probably the least coherent of all the sections of the book. It deals with general principles of support chemistry including the surface structure of supports and the physico-chemical properties of metal oxides. However, it also deals with more specialised areas such as the photochemistry of adsorbed molecules and electrochemistry at modified surfaces. These do however provide a useful interface with related areas such as sensors and conducting polymers. Within Chapters 3-5 in this part a description of some supported reactions is given. The last chapter in Part I, Chapter 6, gives some practical guidance in setting up supported reactions and includes seven detailed experimental procedures. These are likely to prove very useful to new practitioners of the techniques, but might have been included more appropriately as an "experimental" appendix. Part II concentrates on physico-chemical studies of supports and supported species. Chapter 7 is a very useful and concise compilation of surface analysis techniques. So often these are described in such detail and with such enthusiasm by authors that they lose their usefulness to all but the specialist. This is n o t so in this case, and there is something for everyone to learn in the chapter. Chapters 8 and 9 deal with ESR and N M R techniques applied mainly to zeolites and silica, while Chapter 10 covers wider aspects of the physico-chemical characterisation of chemical species on or in zeolites, clays, silica and alumina. Finally, Chapter 11 covers the X-ray crystallography of clays specifically. The treatment is very pictorial and most useful for the "non-clay" and "non-solid state" expert. Part III deals with polymer-supported species, i.e., organic macromolecules as supports. Taken as a group, Chapters 12-14 give a reasonably broad coverage, but obviously
89
Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands
BOOK REVIEWS Publisher's Note: The Publisher received two different reviews of the book Preparative Chemistry Using Supported Reagents. Both are presented below.
Preparative Chem&try Using Supported Reagents, by Pierre Laszlo (Ed.), Academic Press, San Diego, 1987, xiv + 545 pages, ISBN 0-12-437105-1, $110.00.
This book, edited by Pierre Laszlo, contains 27 chapters written by experts in the field. To a practitioner of polymer-supported chemistry, Laszlo's introduction comes as a surprise, as almost no mention is made of polymers. Laszlo traces the origins of the field to heterogeneous catalysis and chromatography, both on inorganic supports, then mentions briefly the example of biochemistry where enzymes provide an ideal model of supramolecular chemistry applicable to the design of new polymer-supported reagents or catalysts. Though Merrifield's solid-phase synthesis and supported enzyme techniques are mentioned in cursory fashion, ion-exchange resins and supported cells are not. In fact, this apparent omission is not inappropriate in the context of a book which has chosen as its main focus chemistry on inorganic supports. Supported reagents based on organic supports are mentioned only very briefly in three chapters, which can only manage to provide a flavor of the field of polymer-supported chemistry. A great strength of the book can be traced to Laszlo's judicious choice of several introductory chapters, which expose various principles of chemistry on solid surfaces that are clearly germane to all supported reactions and add greatly to the overall usefulness of the book.
Thus, in chapter two, Pfeifer offers a concise overview of the principles of fractal surface characterization; this is of great importance to the design of supported reagents and many practitioners in the field of supported chemistry will greatly benefit from reading it. Other early chapters provide insight in the photochemistry of adsorbed molecules and electrochemical synthesis at modified electrode surfaces. Several interesting chapters are devoted to the development and use of physico-chemical methods and tools for the study of surfaces or supported reagents in general. A most useful chapter written by Corn~lis contains a first-hand account of several practical recipes and numerous useful hints for anyone who might wish to set up a reagent supported on inorganic supports such as clay or silica. As mentioned earlier, three individual reviews concerned with polymer-supported chemistry follow, but these are of such limited scope that they can only provide a very fragmentary view of what has been done, or what could be done, using organic supports. Perhaps these chapters should not have been included at all in this book as they do not blend well with the rest of the text. A second strength of the book is its excellent coverage of reagents supported on inorganic materials. This coverage is semi-encyclopedic, covering most of the known applications of reagents based on inorganic supports, with generous references extending to mid-1985. Individual chapters cover the following supports: metal oxides, graphite, alumina, silica, zeolites and clay.
90
Unfortunately perhaps not all chapters include a critical perspective of the field, or suggest future directions. Particularly interesting in this context is Posner's enlightening writing on alumina-supported reagents, or Csicery and Laszlo's crisp account of shapeselective catalysis on zeolites. Overall, this book will be a valuable addition to many synthetic chemists' personal library, as it brings together expertly written, if somewhat concise, reviews of topics which have seldom been considered as a whole. It will not be a primary reference to those concerned with organic reactive polymers, but it will certainly contribute to the development of new and exciting supported chemistry through increased awareness of the variety of supports which are available, their characterization and their uses. JEAN M.J. FRI~CHET
Cornell University
This text of 545 pages is a little unusual because it comprises 27 chapters, each with its own author or authors. On average therefore each contribution is only of about 20 pages. To give the book some overall structure the editor has divided it into eight parts: I. Supported Reagents: General principles II. Physico-Chemical Studies of the Structure of the Solid Supports III. Polymer-supported Reagents IV. Graphite Intercalation Compounds V. Alumina-supported Reagents VI. Silica-supported and Silica-gel-supported Reagents VII. Use of Zeolites and Supports VIII. Clay-activated Organic Reactions The book concentrates primarily on inorganic supports--alumina, silica, zeolites and clays--and deals with polymer-supported systems relatively briefly in only 60 pages--Part III, Chapter 12, 13, and 14. As a
result the text does not overlap unduly with the more specialised texts on polymer-supported species, but rather it complements these quite nicely. Part I is probably the least coherent of all the sections of the book. It deals with general principles of support chemistry including the surface structure of supports and the physico-chemical properties of metal oxides. However, it also deals with more specialised areas such as the photochemistry of adsorbed molecules and electrochemistry at modified surfaces. These do however provide a useful interface with related areas such as sensors and conducting polymers. Within Chapters 3-5 in this part a description of some supported reactions is given. The last chapter in Part I, Chapter 6, gives some practical guidance in setting up supported reactions and includes seven detailed experimental procedures. These are likely to prove very useful to new practitioners of the techniques, but might have been included more appropriately as an "experimental" appendix. Part II concentrates on physico-chemical studies of supports and supported species. Chapter 7 is a very useful and concise compilation of surface analysis techniques. So often these are described in such detail and with such enthusiasm by authors that they lose their usefulness to all but the specialist. This is n o t so in this case, and there is something for everyone to learn in the chapter. Chapters 8 and 9 deal with ESR and N M R techniques applied mainly to zeolites and silica, while Chapter 10 covers wider aspects of the physico-chemical characterisation of chemical species on or in zeolites, clays, silica and alumina. Finally, Chapter 11 covers the X-ray crystallography of clays specifically. The treatment is very pictorial and most useful for the "non-clay" and "non-solid state" expert. Part III deals with polymer-supported species, i.e., organic macromolecules as supports. Taken as a group, Chapters 12-14 give a reasonably broad coverage, but obviously