关于高等有机化学的电子书，最新版本，经典著作，适合工学理学等领域BICENTENNIA18。7WILEY02。07BICENTENNIALTHE WILEY BICENTENNIAL-KNOWLEDGE FOR GENERATIONSach generation has its unique needs and aspirations when charles wiley firstopened his small printing shop in lower Manhattan in 1807, it was a generationof boundless potential searching for an identity. And we were there, helping todefine a new american literary tradition Over half a century later, in the midstof the Second Industrial Revolution, it was a generation focused on building thefuture. Once again, we were there, supplying the critical scientific, technical, andengineering knowledge that helped frame the world. 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For more information about Wiley products, visit our websiteatwww.wiley.comLibrary of Congress Cataloging-in-Publication Data is availableSmith, Michael B, March, JerryMarchs Advanced Organic Chemistry: Reactions, Mechanismsand structure. sixth editionISBN13:978-0-471-72091-1ISBN10:0-471-72091-7Printed in the united states of america10987654321PREFACEOrganic chemistry is a vibrant and growing scientific discipline that touches a vastnumber of scientific areas. This sixth edition of "Marchs Advanced organicChemistry" has been thoroughly updated to reflect new areas of Organic chemistry,as well as new advances in well-known areas of Organic chemistry. Every topicretained from the fifth edition has been brought up to date. Changes include theaddition of a few new sections, significant revision to sections that have seen explo-sive growth in that area of research, moving sections around within the book to better reflect logical and reasonable chemical classifications, and a significant rewriteof much of the book more than 7000 new references have been added. as with thefifth edition when older references were deleted and in cases where a series ofpapers by the same principal author were cited, all but the most recent were deletedThe older citations should be found within the more recent one or ones The fundamental structure of the sixth edition is essentially the same as that of all previousones, although acyl substitution reactions have been moved from chapter 10 tochapter 16. and many oxidation or reduction reactions have been consolidatedinto chapter 19Like the first five editions the sixth is intended to be a textbook for a course inadvanced organic chemistry taken by students who have had the standard undergraduate organic and physical chemistry coursesThe goal as in previous editions is to give equal weight to the three fundamentalaspects of the study of organic chemistry: reactions, mechanisms, and structure. Astudent who has completed a course based on this book should be able to approachthe literature directly, with a sound knowledge of modern basic organic chemistry.Major special areas of organic chemistry: terpenes, carbohydrates, proteins, manyorganometallic reagents, combinatorial chemistry, polymerization and electrochemical reactions, steroids, etc have been treated lightly or ignored completely. Ishare the late Professor Marchs opinion that these topics are best approached afterthe first year of graduate study, when the fundamentals have been mastered, eitherin advanced courses, or directly, by consulting the many excellent books and reviewarticles available on these subjects. In addition, many of these topics are so vast,they are beyond the scope of this bookThe organization is based on reaction types so the student can be shown thatdespite the large number of organic reactions, a relatively few principles sufficeto explain nearly all of them. Accordingly, the reactions-mechanisms section ofthis book(Part 2) is divided into 10 chapters(10-19), each concerned with a dif-ferent type of reaction. In the first part of each chapter the appropriate basicVI PREFACEmechanisms are discussed along with considerations of reactivity and orientation,while the second part consists of numbered sections devoted to individual reactionswhere the scope and the mechanism of each reaction are discussed. Numbered sections are used for the reactions. Since the methods for the preparation of individualclasses of compounds(e. g, ketones, nitriles, etc )are not treated all in one place,index has been provided(Appendix b) by use of which all methods for the prepara-tion of a given type of compound will be found. For each reaction, a list of organicSyntheses references is given where they have been reported. Thus for many reac-tions the student can consult actual examples in Organic syntheses. It is importantto note that the numbers for each reaction differ from one edition to the other, andmany of the sections in the fifth edition do not correlate with the fourth. A correla-tion table is included at the end of this preface that directly correlates the sectionsfound in the 5th edition with the new ones in the 6th editionThe structure of organic compounds is discussed in the first five chapters of Part 1This section provides a necessary background for understanding mechanisms and isalso important in its own right. The discussion begins with chemical bonding andends with a chapter on stereochemistry. There follow two chapters on reactionmechanisms in general, one for ordinary reactions and the other for photochemicalreactions. Part I concludes with two more chapters that give further background tothe study of mechanismsIn addition to reactions mechanisms and structure the student should havesome familiarity with the literature of organic chemistry. a chapter devoted tothis topic has been placed in Appendix a, though many teachers may wish to coverthis material at the beginning of the courseThe IUPAC names for organic transformations are included first introduced inthe third edition Since then the rules have been broadened to cover additionalcases; hence more such names are given in this edition. Furthermore, IUPAC hasnow published a new system for designating reaction mechanisms(see p 420), andsome of the simpler designations are includedIn treating a subject as broad as the basic structures, reactions, and mechanismsof organic chemistry, it is obviously not possible to cover each topic in great depthNor would this be desirable even if possible. Nevertheless, students will often wishto pursue individual topics further. An effort has therefore been made to guide thereader to pertinent review articles and books published since about 1965. In thisrespect, this book is intended to be a guide to the secondary literature(since about1965) of the areas it covers. furthermore in a graduate course students should bencouraged to consult primary sources. To this end, more than 20, 000 references tooriginal papers have been includedAlthough basically designed for a one-year course on the graduate level, thisbook can also be used in advanced undergraduate courses but a one-year coursein organic chemistry prior to this is essential, and a one year course in physicalchemistry is strongly recommended. It can also be adapted by the omission of aarge part of its contents, to a one-semester course. Indeed, even for a one-yearcourse, more is included than can be conveniently covered many individual sections can be easily omitted without disturbing continuityPREFACE VIlThe reader will observe that this text contains much material that is included infirst-year organic and physical chemistry courses, though in most cases it goes moredeeply into each subject and, of course, provides references which first-year textsdo not. It has been my experience that students who have completed the first-yearcourses often have a hazy recollection of the material and greatly profit from arepresentation of the material if it is organized in a different way. It is hoped thatthe organization of the material on reactions and mechanisms will greatly aid thememory and the understanding. In any given course the teacher may want to omitsome chapters because students already have an adequate knowledge of the materialor because there are other graduate courses that cover the areas more thoroughlyChapters l, 4, and 7 especially may fall into one of these categoriesThis book is probably most valuable as a reasonably up-to-date reference workStudents preparing for qualifying examinations and practicing organic chemists wilfind that part 2 contains a survey of what is known about the mechanism and scopeof a large number of reactions, arranged in an orderly manner based on reactiontype and on which bonds are broken and formed. Also valuable for reference pur-poses are the previously mentioned lists of reactions classified by type of compoundprepared(Appendix B)and of all of the Organic Syntheses references to eachreactionAnyone who writes a book such as this is faced with the question of which unitsto use, in cases where international rules mandate one system, but published papersuse another Two instances are the units used for energies and for bond distancesFor energies, IUPAC mandates joules, and many journals do use this unit exclu-sively. However, organic chemists who publish in United States journals overwhel-mingly use calories and this situation shows no signs of changing in the near futureSince previous editions of this book have been used extensively both in this countryand abroad, I have now adopted the practice of giving virtually all energy values inboth calories and joules. The question of units for bond distances is easier toanswer. Although IUPAC does not recommend Angstrom units, nearly all bond dis-tances published in the literature anywhere in the world, whether in organic or incrystallographic journals, are in these units, though a few papers do use picometersTherefore, I continue to use only Angstrom unitsI would like to acknowledge the contributions of those chemists cited andthanked by Professor March in the first four editions. I especially thank GeorgeMajetich, Warren Hehre, and Amos B. Smith Ill for generous contributions to spe-cialized sections in the book as well as reviewing those sections i also thank themany people who have contributed comments or have pointed out errors in the 5thedition that were invaluable to putting together the 6th edition i thank cambridgeSoft InC for providing ChemOffice, with Chem Draw, which was used to prepare allreactions and several structures in this book. i thank dr. Warren hehre and wavefunction, Inc for providing MacSpartan, allowing the incorporation of Spartan 3Dmodels for selected molecules and intermediatesSpecial thanks are due to the Interscience division of John Wiley sons and toDr. Darla Henderson without whose support the book would not have been completed. Special thanks are also given to Shirley Thomas and rebekah Amos atVIIL PREFACEWiley for their fine work as editors in turning the manuscript into the finished bookI also thank ms Jeannette Stiefel, for an excellent job of copy editing the manuscript. i gratefully acknowledge the work of the late Professor Jerry march, uponwhose work this new edition is built, and who is responsible for the concept of thisbook and for carrying it through four very successful editionsI encourage those who read and use the sixth edition to contact me directly withcomments, errors, and with publications that might be appropriate for future edi-tions. I hope that this new edition will carry on the tradition that Professor Marchbegan with the first editionMy Email address ismichael smith @uconn. eduand my homepage ishttp://orgchem.chemuconn.edu/home/mbs-home.htmlFinally, I want to thank my wife Sarah for her patience and understanding duringthe preparation of this manuscript. I also thank my son Steven for his support. Without their support, this work would not have been possibleMICHAEL B. SMITHJune. 2006sth edition -,6th edition10-18—10-1410-35-16-6810-2—→10-210-19—→10-1510-36—10-2410-3—10-310-20→→10-1610-37—10-2510-4—→10-410-21→16-6110-38—10-2610-5—→10-510-22→→16-6210-3916-6910-6—10-610-23-16-6310-40—10-2710-7—→10-710-24→→16-6410-41—→10-2810-8-16-5710-25-16-6510-42—10-29109→16-5810-26-10-1710-43—→10-3010-10→→16-5910-27—10-1810-44—10-3110-11→→16-6010-28—→10-1910-46—10-3210-12—→10-810-29→16-6610-47—10-3310-13—→10-910-30—16-6710-4816-7010-14→10-1010-31—10-2010-49—10-3410-15—10-1110-32—10-2110-50-10-3510-16—10-1210-33-10-2210-51—→10-3710-17—10-1310-34→→10-2310-52—10-38PREFACE IX10-53—10-3910-100一10-6011-19—→11-1910-54—10-4010-101-→10-64l1-20→→11-2010-5516-7210-102—10-6511-21—→11-2110-56→16-7310-103—10-6611-22-11-1210-57—16-7410-104—10-6711-23→→11-1310-5816-7510-105→10-68l1-24—→11-1410-59—16-7610-106—→10-7011-25l1-2210-60→→16-7710-107—→10-7111-26-11-2310-61—→10-4110-108—10-7211-27-11-2410-62→10-4210-109—10-73l1-28-11-2510-63—10-3610-110—→10-74l1-2911-2610-64一→10-4210-111—10-7511-30-11-2710-65—10-4310-112—10-7611-3111-2810-66→10-4410-113—→10-7711-32-11-2910-67—10-4510-114—16-8111-33—11-3010-68-10-4610-115-16-8211-3411-3110-69—10-4710-11616-8311-3511-3210-70—10-4810-11716-8411-36→11-3310-71—10-4910-118-16-8511-37—11-3410-72—10-5010-119→16-8611-38-11-3510-730-5110-120→→16-8711-39-11-3610-74—→10-5210-121→16-8811-40—11-3710-75—10-5310-122→16-89l1-4111-3810-76—10-5410-123→→169011-42—11-3910-77一→16-7910-124—16-10011-43-11-4010-7816-8010-125—16-10111-4411-4110-79→→19-5310-126→16-10210-80→19-5710-127→16-10312-1-→12-110-81→→19-5410-128-16-10412-2→12-210-82→19-5810-129-16-10512-3-12-310-83→196612-4—→12-410-84195611-112-5210-85→19-3511-2→11-212-6→→12-610-86→19-5911-3—11-312-7→→12-710-87→→19-6711-4-11-412-8-12-810-88-19-7012-9—→12-1010-89→→19-39l1-611-612-10→12-1110-90—194011-7—11-712-11-12-1210-91—19-4111-8—11-812-1212-1310-92→10-5511-912-13—→12-1410-93—→10-5611-10—11912-14→→12-1610-94—→10-57l1-11-→11-1012-15—12-1810-9510-5811-12—11-1112-16—→12-1910-96→10-5911-131-1512-17122010-98—→10-6111-1411-1712-18→10-6910-9910-63l1-15→11-1812-19-12-21