《有机化学》课程教学资源（参考书籍）Solvents and Solvent Effects in Organic Chemistry, Third, Updated and Enlarged Edition, 2003, Christian Reichardt

Copyrighted Material WILEY-VCH Christian Reichardt Solvents and Solvent Effects in Organic Chemistry Third, Updated and Enlarged Edition 0Z Copyrighted Material

er Phil pps- n-Marburg cichardt-Marbur This book ments,data,illustrations,procedural details or other items may inadvertently be inaccurate. First Reprint 2004 Library of Congress Card No.:applied for A catalogue record for this book is available from the British Library. hBibotek lists this publication in the DeutscheNa n in u he Nationalbibliografie:detailed biblio- temet at http://dnb ddb.de ISBN3-527-30618-8 2003 WILEY-VCH Verlag GmbH Co.KGaA,Weinheim d on acid-t those of translation b uced in any form part of this book photo y other m ans r trans s.Reg considered unprotectedby law. s book even ch are not to g K Printing:Strauss Offsetdruck GmbH,Morlenbach Printed in the Federal Republic of Germany

Prof. Dr. Christian Reichardt Fachbereich Chemie der Philipps-Universita¨t Marburg Hans-Meerwein-Straße 35032 Marburg Germany e-mail: Reichardt-Marburg@t-online.de This book was carefully produced. Nevertheless, author and publisher do not warrant the infor￾mation contained therein to be free of errors. Readers are advised to keep in mind that state￾ments, data, illustrations, procedural details or other items may inadvertently be inaccurate. First Reprint 2004 Library of Congress Card No.: applied for A catalogue record for this book is available from the British Library. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed biblio￾graphic data is available in the Internet at http://dnb.ddb.de. ISBN 3-527-30618-8 6 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Printed on acid-free paper. All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition: Asco Typesetters, Hong Kong. Printing: Strauss O¤setdruck GmbH, Mo¨rlenbach Bookbinding: J. Scha¨¤er GmbH & Co. KG, Gru¨nstadt Printed in the Federal Republic of Germany

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 expe ntal and theoretical organic chem istry,this im ved third edit n is n esented to the interested re der Following the same layout as in the sec ond edition all to ics retained have beer brought up to date. with smaller and larger chang and additio ns(4.4.7and5.5.13)are ith soly pag dealing host/guest co equilibria and i s in biphasic olvent syste ms and ne olvents ely more than 900 ney added.giving S P and n older olde dded he The list of ea ch chapter he lite th f200i the st nur f pu papers deali ng with solve efects in all ar f orga che didacti oint of uld on selected.Th examples from the this field not a mo The resp apo 0 review d in a certain field reade ffects Great progress has been made during the last decade in theoretical treatments solvent effects by various quantum-chemical meth ods and computational strategie When indicate d,relevant references are given to solution reactions o absorptions. However,a critical evaluation o all the the l models and method 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.symbols.terms.and SI units recom mended by the IUPAC commissions has also been made in this third edition. For comments and valuable suggestions I have to thank many colleagues,in par ticular Prof.E.M.Kosower,Tel Aviv/Israel,Prof.R.G.Makitra,Lviv/Ukraine,Prof N.O.Mchedlov-Petrossyan,Kharkiv/Ukraine,and Prof.K.Mockel,Muhlhausen/ Germany.For their assistance in drawing formulae,preparing the indices,and provid ing me with difficult to obtain literature,I thank Mr.G.Schafer(technician),Mrs.S. Schellenberg (secretary),and Mrs.B.Becht-Schroder (librarian),all at the Department G.J.Leigh. and W V.Met ski- ePublications,London,1998 menclature-A U AC Recom es Units and Symbols in in Physical Organic Chemistry-IUPAC Recommendations Tristan:SI Chemical Data,4th ed.,Wiley,Chichester,1999: Datensammlung Chemie in SI-Einheiten,3d ed.,Wiley-VCH,Weinheim/Germany,1999

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 e¤ects in experimental and theoretical organic chem￾istry, 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 e¤ects on host/guest complexation equilibria and reactions in biphasic solvent systems and neo￾teric solvents, respectively. More than 900 new references have been added, giving pre￾ference 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 e¤ects 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 selec￾tion, apologizes in advance to all chemists whose valuable work on solvent e¤ects 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 e¤ects. Great progress has been made during the last decade in theoretical treatments of solvent e¤ects 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 di¤erential 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) recom￾mended by the IUPAC commissions has also been made in this third edition. For comments and valuable suggestions I have to thank many colleagues, in par￾ticular Prof. E. M. Kosower, Tel Aviv/Israel, Prof. R. G. Makitra, Lviv/Ukraine, Prof. N. O. Mchedlov-Petrossyan, Kharkiv/Ukraine, and Prof. K. Mo¨ckel, Mu¨hlhausen/ Germany. For their assistance in drawing formulae, preparing the indices, and provid￾ing me with di‰cult to obtain literature, I thank Mr. G. Scha¨fer (technician), Mrs. S. Schellenberg (secretary), and Mrs. B. Becht-Schro¨der (librarian), all at the Department 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. Cvitas, K. Homann, N. Kallay, and K. Kuchitsu: Quantities, Units and Symbols in Physical Chemistry, 2nd ed., Blackwell Science Publications, London, 1993. c) P. Mu¨ller: 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

VIII Preface to the Third Edition 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 manu cript,but also for her constant encouragement and support during the writing of this book Marburg (Lahn),Spring 2002 Christian Reichardt

of Chemistry, Philipps University, Marburg/Germany. Special thanks are due to the sta¤ 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 VIII Preface to the Third Edition

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 chemistrv During the last eight vears the study of solvent effects on both chemical reac tions and absc ectra has made much r ss,and nume as interesting and nles have heen dese ibed in In cular the st idy of ionic reactions in the ga s phase ow po ssible due to r mental techniau has allowed direct co ons be s-p actions.This has led to a gre ter arged to ng of solut equent apters 4 and 5 hav nclude a description o of ioni c gas-phase reactions compare ed to t the The of well-studied solvent-de nden ses abso on,has increase 1979.0n ,Le.reaction and y a re more instructive,recently studi d examples could be included in this secon d The search for empirical ters of solvent ity and their application in mul s recently been intensified,thus making it necessary to arge parts e Spe tention n give the chemical phys solvents common in daily labora ry wort and refore,al Appendi mproved:sor e have been completely replaced by new A new well-refere nced table on solvent-drying has be en added(Table A-3).Chapte 3 has been enlarged,in parti ular by the inclusion of sol vent classi ations using multivariate s tistical methods (Section 3.5).All these amendments justify the change in the title of the book to Soltents 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.comment and valuable suggestions.Especially helpful suggestions came from Professors H-D.Forsterling. Marburg,J.Shorter,Hull/England,and R.I.Zalewski,Poznani/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 prepara- tion of this edition and for her help with the indices. Marburg(Lahn),Spring 1988 Christian reichardt ◆Cf.Pure Appl..Chem.5,1(1979：外ibid.53,753(1981:ibid.55,1281(1983 )ibid.57,105 (1985)

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 e¤ects on both chemical reac￾tions 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 sta￾tistical methods (Section 3.5). All these amendments justify the change in the title of the book to Solvents and Solvent E¤ects 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. Fo¨rsterling, Marburg, J. Shorter, Hull/England, and R. I. Zalewski, Poznan´/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 prepara￾tion 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)