Solvents and Solvent Effects in Organic Chemistry E-Book

Christian Reichardt

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1624

Veröffentlichungsjahr: 2011

Beschreibung

Now in its 4th edition, this book remains the ultimate reference for all questions regarding solvents and solvent effects in organic chemistry. Retaining its proven concept, there is no other book which covers the subject in so much depth, the handbook is completely updated and contains 15% more content, including new chapters on "Solvents and Green chemistry", "Classification of Solvents by their Environmental Impact", and "Ionic Liquids".
An essential part of every organic chemist's library.

Leseprobe

Contents

1 Introduction

2 Solute-Solvent Interactions

2.1 Solutions

2.2 Intermolecular Forces [26, 27, 182-184]

2.3 Solvation [49, 85–98, 98a, 233–241]

2.4 Preferential Solvation [89, 94, 96, 118–120, 241, 249, 250]

2.5 Micellar Solvation (Solubilization) [96, 128, 130-132, 220, 262-267]

2.6 Ionization and Dissociation [49, 96, 134-139, 241, 278, 279]

3 Classification of Solvents

3.1 Classification of Solvents according to Chemical Constitution

3.2 Classification of Solvents using Physical Constants

3.3 Classification of Solvents in Terms of Acid-Base Behaviour

3.4 Classification of Solvents in Terms of Specific Solute/Solvent Interactions

3.5 Classification of Solvents using Multivariate Statistical Methods

4 Solvent Effects on the Position of Homogeneous Chemical Equilibria

4.1 General Remarks

4.2 Solvent Effects on Acid/Base Equilibria [8-13]

4.3 Solvent Effects on Tautomeric Equilibria

4.4 Solvent Effects on Other Equilibria

5 Solvent Effects on the Rates of Homogeneous Chemical Reactions

5.1 General Remarks [1-29, 452-463]

5.2 Gas-Phase Reactivities

5.3 Qualitative Theory of Solvent Effects on Reaction Rates

5.4 Quantitative Theories of Solvent Effects on Reaction Rates

5.5 Specific Solvation Effects on Reaction Rates

6 Solvent Effects on the Absorption Spectra of Organic Compounds

6.1 General Remarks

6.2 Solvent Effects on UV/Vis Spectra [5-17]

6.3 Solvent Effects on Infrared Spectra

6.4 Solvent Effects on Electron Spin Resonance Spectra

6.5 Solvent Effects on Nuclear Magnetic Resonance Spectra

7 Empirical Parameters of Solvent Polarity

7.1 Linear Gibbs Energy Relationships

7.2 Empirical Parameters of Solvent Polarity from Equilibrium Measurements

7.3 Empirical Parameters of Solvent Polarity from Kinetic Measurements

7.4 Empirical Parameters of Solvent Polarity from Spectroscopic Measurements

7.5 Empirical Parameters of Solvent Polarity from Other Measurements

7.6 Interrelation and Application of Solvent Polarity Parameters

7.7 Multiparameter Approaches

8 Solvents and Green Chemistry

8.1 Green Chemistry

8.2 Reduction of Solvent Use

8.3 Green Solvent Selection

8.4 Non-Traditional Solvents

8.5 Outlook

Appendix A. Properties, Purification, and Use of Organic Solvents

A.1 Physical Properties

A.2 Purification of Organic Solvents

A.3 Spectroscopic Solvents

A.4 Solvents as Reaction Media

A.5 Solvents for Recrystallization

A.6 Solvents for Extraction and Partitioning (Distribution)

A.7 Solvents for Adsorption Chromatography

A.8 Solvents for Acid/Base Titrations in Non-Aqueous Media

A.9 Solvents for Electrochemistry

A.10 Toxicity of Organic Solvents

References

Figure and Table Credits

Subject Index

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The Authors

Prof. Dr. Christian ReichardtFachbereich Chemieder Philipps-UniversitätHans-Meerwein-Strasse35032 Marburg, Germany

Prof. Dr. Thomas WeltonDepartment of ChemistryImperial College LondonSouth Kensington CampusLondon SW7 2AZUnited Kingdom

Cover

Previous Editions1st Edition 19792nd Edition 19881st Reprint 19903rd Edition 20031st Reprint 20042nd Reprint 20054th Edition 2011

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To Mariaand in memory of my parents

C. R.

To Mikeand my parents

T. W.

Preface to the Fourth Edition

About 40 years ago, in 1969, a German paperback entitled Lösungsmitteleffekte in der organischen Chemie, written by the first author, was published by Verlag Chemie in Weinheim. Based on this paperback and its second edition in 1973, an enlarged English edition called Solvent Effects in Organic Chemistry appeared in 1979, followed by a second English edition in 1988 with the now enlarged title Solvents and Solvent Effects in Organic Chemistry. A first and second reprint in 2004 and 2005 of the third, updated and enlarged English edition of this book, published in 2003, demonstrate the continuing common interest in the study of solvent effects on chemical reactions and physical processes. This and the progress that has been made in recent years in this field of research encouraged us to present now to the interested reader a fourth, again updated and enlarged, edition of this book. This was only possible because a junior author helped the meanwhile retired senior author with the preparation of the manuscript for this new edition, particularly in writing the new Chapter 8.

This new chapter deals with the relationship between solvents and green chemistry, the classification of solvents by their environmental impact, and the replacement of traditional by non-traditional solvents for chemical reactions.

During the seven years after publication of the third edition in 2003, the number of solvent-dependent processes studied has increased to such an extent (particularly in the field of ionic liquids) that only a careful selection of instructive and representative examples could be additionally included in this fourth edition. The literature has been covered up to 2009, partly up to 2010. New references have been added at the end of the reference list of each chapter.

Consistent use of the nomenclaturea), symbolsb), termsc) and SI unitsd) recommended by the respective IUPAC Commissions has again been made in this fourth edition.

For useful comments and valuable suggestions we thank many colleagues, in particular Prof. Dr. N. O. Mchedlov-Petrossyan, Kharkov/Ukraine, Dr. T. Rager, Basel/Switzerland, and Prof. Dr. G. N. Papatheodorou, Rio/Greece. For their assistance in providing us with difficult to obtain literature and in preparing the final manuscript, C. R. thanks Mrs. B. Becht-Schröder (librarian) and Mr. G. Schäfer (technician) of the Department of Chemistry, Marburg, and also Mrs. Maria Reichardt, Marburg, for her continuous support of this project. T.W. thanks the final-year Imperial College Chemistry students and Green Chemistry Master students for helpful discussions.

We both express our thanks to the staff of Wiley-VCH Verlag GmbH, Weinheim, particularly to Dr. Elke Maase and Dr. Stefanie Volk, for their help and excellent work in turning the manuscript into this final book.

Marburg (Lahn)LondonSummer 2010 Christian ReichardtThomas Welton

a) G. J. Leigh, H. A. Favre, and W. V. Metanomski: Principles of Chemical Nomenclature – A Guide to IUPAC Recommendations, Blackwell, Oxford, 1998; R. Panico, W. H. Powell, and J.-C. Richer: A Guide to IUPAC Nomenclature of Organic Compounds – Recommendations 1993, Blackwell, Oxford, 1993.

b) E. R. Cohen, T. Cvitaš, J. G. Frey, B. Holmström, K. Kuchitsu, R. Marquardt, I. Mills, F. Pavese, M. Quack, J. Stohner, H. L. Strauss, M. Takami, and A. J. Thor: Quantities, Units and Symbols in Physical Chemistry (IUPAC 2007),3rd ed., Royal Society of Chemistry, Cambridge, 2007.

c) P. Müller: Glossary of Terms Used in Physical Organic Chemistry – IUPAC Recommendations 1994, Pure Appl. Chem. 66, 1077 (1994).

d) G. H. Aylward and T. J. V. Findlay: SI Chemical Data,6th ed., Wiley, Milton/Australia, 2008; see also Bureau International des Poids et Mesures (BIPM): Le Système International d’Unités (SI),8th ed., STEDI Media, Paris, 2006.

Preface to the Third Edition

Meeting the demand for the second edition of this book, which is – despite a reprint in 1990 – no longer available, and considering the progress that has been made during the last decade in the study of solvent effects in experimental and theoretical organic chemistry, this improved third edition is presented to the interested reader.

Following the same layout as in the second edition, all topics retained have been brought up to date, with smaller and larger changes and additions on nearly every page. Two Sections (4.4.7 and 5.5.13) are completely new, dealing with solvent effects on host/guest complexation equilibria and reactions in biphasic solvent systems and neoteric solvents, respectively. More than 900 new references have been added, giving preference to review articles, and many older ones have been deleted. New references either replace older ones or are added to the end of the respective reference list of each chapter. The references cover the literature up to the end of 2001.

From the vast number of published papers dealing with solvent effects in all areas of organic chemistry, only some illustrative examples from the didactic and systematic point of view could be selected. This book is not a monograph covering all relevant literature in this field of research. The author, responsible for this subjective selection, apologizes in advance to all chemists whose valuable work on solvent effects is not mentioned in this book. However, using the reviews cited, the reader will find easy access to the full range of papers published in a certain field of research on solvent effects.

Great progress has been made during the last decade in theoretical treatments of solvent effects by various quantum-chemical methods and computational strategies. When indicated, relevant references are given to the respective solution reactions or absorptions. However, a critical evaluation of all the theoretical models and methods used to calculate the differential solvation of educts, activated complexes, products, ground and excited states, is outside the expertise of the present author. Thus, a book on all kinds of theoretical calculations of solvent influences on chemical reactions and physical absorptions has still to be written by someone else.

Consistent use of the nomenclature,a) symbols,b) terms,c) and SI unitsd) recommended by the IUPAC commissions has also been made in this third edition.

For comments and valuable suggestions I have to thank many colleagues, in particular Prof. E. M. Kosower, Tel Aviv/Israel, Prof. R. G. Makitra, Lviv/Ukraine, Prof. N. O. Mchedlov-Petrossyan, Kharkiv/Ukraine, and Prof. K. Möckel, Mühlhausen/Germany. For their assistance in drawing formulae, preparing the indices, and providing me with difficult to obtain literature, I thank Mr. G. Schäfer (technician), Mrs. S. Schellenberg (secretary), and Mrs. B. Becht-Schröder (librarian), all at the Department of Chemistry, Philipps University, Marburg/Germany. Special thanks are due to the staff of Wiley-VCH Verlag GmbH, Weinheim/Germany, particularly to Dr. Elke Westermann, for their fine work in turning the manuscript into the final book. Lastly, my biggest debt is to my wife Maria, not only for her assistance in the preparation of the manuscript, but also for her constant encouragement and support during the writing of this book.

Marburg (Lahn), Spring 2002 Christian Reichardt

a) G. J. Leigh, H. A. Favre, and W. V. Metanomski: Principles of Chemical Nomenclature – A Guide to IUPAC Recommendations, Blackwell Science Publications, London, 1998.

b) I. Mills, T. Cvitaš, K. Homann, N. Kallay, and K. Kuchitsu: Quantities, Units and Symbols in Physical Chemistry,2nd ed., Blackwell Science Publications, London, 1993.

c) P. Müller: Glossary of Terms used in Physical Organic Chemistry – IUPAC Recommendations 1994, Pure Appl. Chem. 66, 1077 (1994).

d) G. H. Aylward and T. J. V. Tristan: SI Chemical Data,4th ed., Wiley, Chichester, 1999; Datensammlung Chemie in SI-Einheiten,3rd ed., Wiley-VCH, Weinheim/Germany, 1999.

Preface to the Second Edition

The response to the first English edition of this book, published in 1979, has been both gratifying and encouraging. Its mixed character, lying between that of a monograph and a textbook, has obviously made it attractive to both the industrial and academic chemist as well as the advanced student of chemistry.

During the last eight years the study of solvent effects on both chemical reactions and absorption spectra has made much progress, and numerous interesting and fascinating examples have been described in the literature. In particular, the study of ionic reactions in the gas phase – now possible due to new experimental techniques – has allowed direct comparisons between gas-phase and solution reactions. This has led to a greater understanding of solution reactions. Consequently, Chapters 4 and 5 have been enlarged to include a description of ionic gas-phase reactions compared to their solution counterparts.

The number of well-studied solvent-dependent processes, i.e. reactions and absorptions in solution, has increased greatly since 1979. Only a representative selection of the more instructive, recently studied examples could be included in this second edition.

The search for empirical parameters of solvent polarity and their applications in multiparameter equations has recently been intensified, thus making it necessary to rewrite large parts of Chapter 7.

Special attention has been given to the chemical and physical properties of organic solvents commonly used in daily laboratory work. Therefore, all Appendix Tables have been improved; some have been completely replaced by new ones. A new well-referenced table on solvent-drying has been added (Table A-3). Chapter 3 has been enlarged, in particular by the inclusion of solvent classifications using multivariate statistical methods (Section 3.5). All these amendments justify the change in the title of the book to Solvents and Solvent Effects in Organic Chemistry.

The references have been up-dated to cover literature appearing up to the first part of 1987. New references were added to the end of the respective reference list of each chapter from the first edition.

Consistent use of the nomenclature, symbols, terms, and SI units recommended by the IUPAC commissions has also been made in the second edition.*)

I am very indebted to many colleagues for corrections, comments, and valuable suggestions. Especially helpful suggestions came from Professors H.-D. Försterling, Marburg, J. Shorter, Hull/England, and R. I. Zalewski, Poznań/Poland, to whom I am very grateful. For critical reading of the whole manuscript and the improvement of my English I again thank Dr. Edeline Wentrup-Byrne, now living in Brisbane/Australia. Dr. P.-V. Rinze, Marburg, and his son Lars helped me with the author index. Finally, I would like to thank my wife Maria for her sympathetic assistance during the preparation of this edition and for her help with the indices.

Marburg (Lahn), Spring 1988 Christian Reichardt

*Cf. Pure Appl. Chem. 51, 1 (1979); ibid. 53, 753 (1981); ibid. 55, 1281 (1983); ibid. 57, 105 (1985).

Preface to the First Edition

The organic chemist usually works with compounds which possess labile covalent bonds and are relatively involatile, thereby often rendering the gas-phase unsuitable as a reaction medium. Of the thousands of reactions known to occur in solution only few have been studied in the gas-phase, even though a description of reaction mechanisms is much simpler for the gas-phase. The frequent necessity of carrying out reactions in the presence of a more or less inert solvent results in two main obstacles: The reaction depends on a larger number of parameters than in the gas-phase. Consequently, the experimental results can often be only qualitatively interpreted because the state of aggregation in the liquid phase has so far been insufficiently studied. On the other hand, the fact that the interaction forces in solution are much stronger and more varied than in the gas-phase, permits to affect the properties and reactivities of the solute in manifold modes.

Thus, whenever a chemist wishes to carry out a chemical reaction he not only has to take into consideration the right reaction partners, the proper reaction vessels, and the appropriate reaction temperature. One of the most important features for the success of the planned reaction is the selection of a suitable solvent. Since solvent effects on chemical reactivity have been known for more than a century, most chemists are now familiar with the fact that solvents may have a strong influence on reaction rates and equilibria. Today, there are about three hundred common solvents available, nothing to say of the infinite number of solvent mixtures. Hence the chemist needs, in addition to his intuition, some general rules and guiding-principles for this often difficult choice.

The present book is based on an earlier paperback ‘‘Lösungsmitteleffekte in der organischen Chemie’’ [1], which, though following the same layout, has been completely rewritten, greatly expanded, and brought up to date. The book is directed both toward the industrial and academic chemist and particularly the advanced student of chemistry, who on the one hand needs objective criteria for the proper choice of solvent but on the other hand wishes to draw conclusions about reaction mechanisms from the observed solvent effects.

A knowledge of the physico-chemical principles of solvent effects is required for proper bench-work. Therefore, a description of the intermolecular interactions between dissolved molecules and solvent is presented first, followed by a classification of solvents derived therefrom. Then follows a detailed description of the influence of solvents on chemical equilibria, reaction rates, and spectral properties of solutes. Finally, empirical parameters of solvent polarity are given, and in an appendix guidelines to the everyday choice of solvents are given in a series of Tables and Figures.

The number of solvent systems and their associated solvent effects examined is so enormous that a complete description of all aspects would fill several volumes. For example, in Chemical Abstracts, volume 85 (1976), approximately eleven articles per week were quoted in which the words ‘‘Solvent effects on...’’ appeared in the title. In the present book only a few important and relatively well-defined areas of general importance have been selected. The book has been written from the point of view of practical use for the organic chemist rather than from a completely theoretical one.

In the selection of the literature more recent reviews were taken into account mainly. Original papers were cited in particular from the didactic point of view rather than priority, importance or completeness. This book, therefore, does not only have the character of a monograph but also to some extent that of a textbook. In order to help the reader in his use of the literature cited, complete titles of the review articles quoted are given. The literature up until December 1977 has been considered together with a few papers from 1978. The use of symbols follows the recommendations of the Symbols Committee of the Royal Society, London, 1971 [2].

I am very grateful to Professor Karl Dimroth, Marburg, who first stimulated my interest in solvent effects in organic chemistry. I am indebted to Professors W. H. Pirkle, Urbana/Illinois, D. Seebach, Zürich/Switzerland, J. Shorter, Hull/England, and numerous other colleagues for helpful advice and information. Thanks are also due to the authors and publishers of copyrighted materials reproduced with their permission (cf. Figure and Table credits on page 495). For the careful translation and improvement of the English manuscript I thank Dr. Edeline Wentrup-Byrne, Marburg. Without the assistance and patience of my wife Maria, this book would not have been written.

Marburg (Lahn), Summer 1978 Christian Reichardt

References

[1] C. Reichardt: Lösungsmitteleffekte in der organischen Chemie.2nd edition. Verlag Chemie, Weinheim 1973;Effets de solvant en chimie organique (translation of the first-mentioned title into French, by Tkatchenko), Flammarion, Paris 1971;Rastvoriteli v organicheskoi khimii (translation of the first-mentioned title into Russian, by E. R. Zakhsa), Izdatel’stvo Khimiya, Leningrad 1973.

[2] Quantities, Units, and Symbols, issued by The Symbols Committee of the Royal Society, London, in 1971.

“Agite, Auditores ornatissimi, transeamus alacres ad aliud negotii! quum enim sic satis excusserimus ea quatuor Instrumenta artis, et naturae, quae modo relinquimus, videamus quintum genus horum, quod ipsi Chemiae fere proprium censetur, cui certe Chemistae principem locum prae omnibus assignant, in quo se jactant, serioque triumphant, cui artis suae, prae aliis omnibus effectus mirificos adscribunt. Atque illud quidem Menstruum vocaverunt.”*)

Hermannus Boerh−ve (1668–1738)

De menstruis dictis in chemia, in:

Elementa Chemiae (1733) [1, 2].

1

Introduction

The development of our knowledge of solutions reflects to some extent the development of chemistry itself [3]. Of all known substances, water was the first to be considered as a solvent. As far back as the time of the Greek philosophers there was speculation about the nature of solution and dissolution. The Greek alchemists considered all chemically active liquids under the name ‘‘Divine water’’. In this context the word ‘‘water’’ was used to designate everything liquid or dissolved. The Greek philosopher Thales of Miletus ( 640–546 bc) asserted that water is the origin out of which everything arose and into everything resolved itself.